Method of making an optical article with an inkjet printing device

ABSTRACT

A method of making an optical article having multiple light-influencing zones can include: forming an alignment coating layer having a first alignment region and a second alignment region over at least a portion of an optical element; applying at least one anisotropic material over the first alignment region and the second alignment region by an inkjet printing device; and applying at least one dichroic material and/or at least one photochromic-dichroic material over at least one of the first alignment region and the second alignment region to form a first light-influencing zone over the first alignment region and a second light-influencing zone over the second alignment region.

CROSS-REFERENCE TO RELATED APPLICATION

This application is the United States national phase of InternationalApplication No. PCT/US2015/058367 filed Oct. 30, 2015, the disclosure ofwhich is hereby incorporated in its entirety by reference.

FIELD OF THE INVENTION

The present invention relates generally to optical articles forinfluencing light and methods of the making optical articles forinfluencing light.

BACKGROUND OF THE INVENTION

Polarizing optical articles, such as sunglasses, can reduce glare due tolight reflected off of surfaces such as pavement, water, and buildings.Thus, the use of polarizing optical articles can enhance vision underglare conditions.

Linearly polarizing lenses, such as for sunglasses, are typically formedfrom stretched polymer sheets comprising a dye to give the lensespolarizing properties. Further, conventional sunglasses are typicallytinted. The polarization and tinted effects on sunglasses can be formedby a number of types of dyes including, dichroic dyes, photochromicdyes, and photochromic-dichroic dyes. These types of dyes can be usedindividually, or in combination, to give the lenses the desiredpolarizing or tinted effects. Dichroic dyes generally provide a fixedpolarization, fixed tint effect, meaning actinic radiation is not neededto make the lenses tinted and polarizing. Photochromic dyes generallyprovided reversible tinting, meaning that the lenses are tinted whenexposed to actinic radiation, and revert to being untinted in theabsence of actinic radiation. Photochromic-dichroic dyes generallyprovide reversible tinting and reversible polarization, based onexposure to actinic radiation.

Liquid crystal displays are prevalent in today's commonly usedtechnology. They can be found, for instance, on tablets, cellphones, cardashboards, and screens at gas stations. Most of these liquid crystaldisplay panels are linearly polarized panels aligned in the verticaldirection. Therefore, those who wear the above-described polarizedsunglasses often cannot see the contents of these liquid crystal displaypanels because of the cross polarization between the vertical alignmentof the panels and the horizontal alignment of the sunglasses. Evenliquid crystal displays having circularly polarized panels are harder tosee while wearing polarizing sunglasses.

Accordingly, it would be advantageous to provide polarizing opticalarticles having more than one zone of different polarizing and opticalproperties to allow enhanced vision in more than one everydayenvironment.

SUMMARY OF THE INVENTION

The present invention is directed to a method of making an opticalarticle having multiple light-influencing zones. The method includes:forming an alignment coating layer comprising a first alignment regionand a second alignment region over at least a portion of an opticalelement; applying at least one anisotropic material over the firstalignment region and the second alignment region by an inkjet printingdevice; and applying at least one dichroic material and/or at least onephotochromic-dichroic material over at least one of the first alignmentregion and the second alignment region to form a first light-influencingzone over the first alignment region and a second light-influencing zoneover the second alignment region.

The present invention is also directed to a method of making an opticalarticle having multiple light-influencing zones. The method includes:forming an alignment coating layer over at least a portion of an opticalelement; applying an anisotropic material over the alignment coatinglayer by an inkjet printing device; and applying at least one of adichroic material and a photochromic-dichroic material over thealignment coating layer in a predetermined pattern to form at least twolight-influencing zones in the predetermined pattern.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates an ophthalmic lens with uniform color/tint andgradient polarization over the entire top surface in accordance with thepresent invention;

FIG. 2 illustrates an ophthalmic lens having a first light influencingzone with a high degree of horizontal polarization formed over an upperportion of the top surface and a second light influencing zone with nopolarization formed over a lower portion of the top surface inaccordance with the present invention;

FIG. 3 illustrates an ophthalmic lens having first light influencingzones with vertical polarization formed over the side portions of thetop surface and a second light influencing zone with horizontalpolarization formed over a central portion of the top surface betweenthe first light influencing zones in accordance with the presentinvention;

FIG. 4 illustrates an ophthalmic lens having first light influencingzones with vertical polarization formed over the side portions of thetop surface, a second light influencing zone with horizontalpolarization formed over an upper portion of the top surface between thefirst light influencing zones, and a third light influencing zone withno polarization formed over a lower portion of the top surface betweenthe first light influencing zones in accordance with the presentinvention;

FIG. 5 illustrates an ophthalmic lens having a first light influencingzone with gradient polarization and gradient tint formed over an upperportion of the top surface and a second light influencing zone with alesser degree/magnitude of gradient polarization and gradient tintformed over a lower portion of the top surface;

FIG. 6 illustrates an ophthalmic lens and an inkjet printer fluidlyconnected to sources containing anisotropic materials, dichroicmaterials, photochromic materials, photochromic-dichroic materials,and/or conventional dyes;

FIG. 7 illustrates an optical article having a gradient tint and agradient polarization;

FIGS. 8A-8E are block diagrams illustrating exemplary methods for makingan optical article having a gradient tint and a gradient polarization;

FIGS. 9A-9E are block diagrams illustrating exemplary methods for makingan optical article having a gradient tint and a gradient polarization;

FIGS. 10A-10D illustrate an optical article having an anisotropiccoating layer suspended over a bath comprising dye solution to contactthe anisotropic coating layer with the dye solution by a dip dye method;

FIGS. 11A-11B illustrate an optical article having an anisotropiccoating layer suspended over a bath comprising dye solution to contactthe anisotropic coating layer with the dye solution by a dip dye method;

FIG. 12 illustrates an optical article having an anisotropic coatinglayer submerged in a bath comprising dye solution to contact theanisotropic coating layer with the dye solution by a dip dye method;

FIG. 13 illustrates an optical article having an anisotropic coatinglayer being contacted by a dye transfer substrate comprising a gradientlayer of dye composition;

FIG. 14 illustrates a kit for making an optical article having agradient tint and a gradient polarization;

FIG. 15 is a photograph of a lens illuminated from behind withunpolarized light, exhibiting a visible tint gradient;

FIG. 16 is a photograph of the lens of FIG. 15 showing the passage oflight through the lens when a polarizer which is oriented parallel (0°)to the alignment of the anisotropic coating layer;

FIG. 17 is a photograph of the lens of FIG. 15 showing the passage oflight through the lens when the polarizer is oriented perpendicular(90°) to the direction of alignment of the anisotropic coating layer;

FIG. 18 is a photograph of a lens illuminated from behind withunpolarized light, exhibiting a uniform tint;

FIG. 19 is a photograph of the lens of FIG. 18 showing the passage oflight through the lens when a polarizer which is oriented parallel (0°)to the alignment of the anisotropic coating layer;

FIG. 20 is a photograph of the lens of FIG. 18 showing the passage oflight through the lens when the polarizer is oriented perpendicular(90°) to the direction of alignment of the anisotropic coating layer;

FIG. 21 is a photograph showing the passage of light through a lens whena polarizer which is oriented parallel (0°) to the alignment of theanisotropic coating layer; and

FIG. 22 shows the passage of light through the lens of FIG. 21 when thepolarizer is oriented perpendicular (90°) to the direction of alignmentof the anisotropic coating layer.

DESCRIPTION OF THE INVENTION

For purposes of the following detailed description, it is to beunderstood that the invention may assume various alternative variationsand step sequences, except where expressly specified to the contrary.Moreover, other than in any operating examples, or where otherwiseindicated, all numbers expressing, for example, quantities ofingredients used in the specification and claims are to be understood asbeing modified in all instances by the term “about”. Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties to be obtained by the presentinvention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard variation found in theirrespective testing measurements.

Also, it should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between (andincluding) the recited minimum value of 1 and the recited maximum valueof 10, that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10.

In this application, the use of the singular includes the plural andplural encompasses singular, unless specifically stated otherwise. Inaddition, in this application, the use of “or” means “and/or” unlessspecifically stated otherwise, even though “and/or” may be explicitlyused in certain instances. Further, in this application, the use of “a”or “an” means “at least one” unless specifically stated otherwise.

All documents, such as, but not limited to, issued patents and patentapplications, referred to herein, and unless otherwise indicated, are tobe considered to be “incorporated by reference” in their entirety.

The present invention is directed to optical articles and methods ofmaking optical articles. The optical articles of the present inventioncomprise at least one optical element coated with at least one coatinglayer. As used herein, the term “optical” means pertaining to orassociated with light and/or vision. For example, the optical articlecan include an optical element including, but not limited to, ophthalmicelements and devices, display elements and devices, windows, mirrors,and the like. The term “ophthalmic” means pertaining to or associatedwith the eye and vision. Non-limiting examples of ophthalmic elementsinclude corrective and non-corrective lenses, including single vision ormulti-vision lenses, which may be either segmented or non-segmentedmulti-vision lenses (such as, but not limited to, bifocal lenses,trifocal lenses, and progressive lenses), as well as other elements usedto correct, protect, or enhance (cosmetically or otherwise) vision,including without limitation, contact lenses, intra-ocular lenses,magnifying lenses, and protective lenses or visors. As used herein theterm “display” means the visible or machine-readable representation ofinformation in words, numbers, symbols, designs, or drawings.Non-limiting examples of display elements and devices include screens,monitors, and security elements, such as security marks. As used hereinthe term “window” means an aperture adapted to permit the transmissionof radiation therethrough. Non-limiting examples of windows includeautomotive and aircraft transparencies, filters, shutters, and opticalswitches. As used herein, the term “mirror” means a surface thatspecularly reflects a large fraction of incident light.

Further, the optical element can comprise a transparent optical element,a reflective optical element, or an optical element with bothtransparent and reflective properties. As used herein, the term“transparent” refers to a material that transmits rays of visible lightin such a way that the human eye may see through the materialdistinctly, and the term “reflective” refers to a material thatredirects visible light away from the material rather than transmittingor absorbing the visible light. To provide an optical element with atleast some reflective properties, a reflective coating can be applied.For instance, a reflective aluminum coating can be applied to at least aportion of the optical element to prepare an optical security elementwith at least some reflective properties.

The optical elements that form the optical article can have variousshapes including, but not limited to, round, flat, cylindrical,spherical, planar, substantially planar, plano-concave and/orplano-convex, curved, including, but not limited to, convex, and/orconcave.

In general, the optical element can be made of various materialsincluding, but not limited to, organic materials, inorganic materials,or combinations thereof (for example, composite materials).

Specific, non-limiting examples of organic materials that may be used toform the optical element disclosed herein include polymeric materials,for example, homopolymers and copolymers, prepared from the monomers andmixtures of monomers disclosed in U.S. Pat. No. 5,962,617 and in U.S.Pat. No. 5,658,501 from column 15, line 28 to column 16, line 17, thedisclosures of which U.S. patents are specifically incorporated hereinby reference. For example, such polymeric materials can be thermoplasticor thermoset polymeric materials, can be transparent or optically clear,and can have any refractive index required. Non-limiting examples ofsuch disclosed monomers and polymers include: polyol(allylcarbonate)monomers, e.g., allyl diglycol carbonates such as diethyleneglycol bis(allyl carbonate), which monomer is sold under the trademarkCR-39 by PPG Industries, Inc.; polyurea-polyurethane(polyurea-urethane)polymers, which are prepared, for example, by thereaction of a polyurethane prepolymer and a diamine curing agent, acomposition for one such polymer being sold under the trademark TRIVEXby PPG Industries, Inc.; polyol(meth)acryloyl terminated carbonatemonomer; diethylene glycol dimethacrylate monomers; ethoxylated phenolmethacrylate monomers; diisopropenyl benzene monomers; ethoxylatedtrimethylol propane triacrylate monomers; ethylene glycolbismethacrylate monomers; poly(ethylene glycol)bismethacrylate monomers;urethane acrylate monomers; poly(ethoxylated bisphenol Adimethacrylate); poly(vinyl acetate); poly(vinyl alcohol); poly(vinylchloride); poly(vinylidene chloride); polyethylene; polypropylene;polyurethanes; polythiourethanes; thermoplastic polycarbonates, such asthe carbonate-linked resin derived from bisphenol A and phosgene, onesuch material being sold under the trademark LEXAN; polyesters, such asthe material sold under the trademark MYLAR; poly(ethyleneterephthalate); polyvinyl butyral; poly(methyl methacrylate), such asthe material sold under the trademark PLEXIGLAS, and polymers preparedby reacting polyfunctional isocyanates with polythiols or polyepisulfidemonomers, either homopolymerized or co- and/or terpolymerized withpolythiols, polyisocyanates, polyisothiocyanates, and optionallyethylenically unsaturated monomers or halogenated aromatic-containingvinyl monomers. Also contemplated are copolymers of such monomers andblends of the described polymers and copolymers with other polymers, forexample, to form block copolymers or interpenetrating network products.

Non-limiting examples of inorganic materials suitable for use in formingthe optical elements include glasses, minerals, ceramics, and metals.For example, the optical element can comprise glass. As indicated above,a reflective coating or layer can be deposited or otherwise applied to asurface of an inorganic or an organic optical element to make itreflective or to enhance its reflectivity.

Still further, the optical elements can be untinted, tinted, linearlypolarizing, circularly polarizing, elliptically polarizing,photochromic, or tinted-photochromic substrates. As used herein, withreference to optical element substrates, the term “untinted” meanssubstrates that are essentially free of coloring agent additions (suchas, but not limited to, conventional dyes) and have an absorptionspectrum for visible radiation that does not vary significantly inresponse to actinic radiation. Further, with reference to opticalelement substrates, the term “tinted” means substrates that have acoloring agent addition (such as, but not limited to, conventional dyes)and an absorption spectrum for visible radiation that does not varysignificantly in response to actinic radiation. It is appreciated thatsimilar properties can be provided by applying a particular coating(s)onto the optical element, which is explained in further detail herein.

As used herein, the term “linearly polarizing” with reference tosubstrates refers to substrates that are adapted to linearly polarizeradiation (i.e., confine the vibrations of the electric vector of lightwaves to one direction). As used herein, the term “circularlypolarizing” with reference to substrates refers to substrates that areadapted to circularly polarize radiation. As used herein, the term“elliptically polarizing” with reference to substrates refers tosubstrates that are adapted to elliptically polarize radiation. Further,as used herein, with reference to substrates, the term“tinted-photochromic” means substrates containing a coloring agentaddition as well as a photochromic material, and having an absorptionspectrum for visible radiation that varies in response to at leastactinic radiation. Thus, for example and without limitation, thetinted-photochromic substrate can have a first color characteristic ofthe coloring agent and a second color characteristic of the combinationof the coloring agent the photochromic material when exposed to actinicradiation.

As indicated, the optical articles of the present invention also includeat least one coating applied over at least a portion of the opticalelement. The coating can be applied over at least a portion of at leastone major surface of the optical element. The coating can also beapplied over the entire surface of the optical element.

As used herein, the term “coating” means a supported film derived from aflowable composition, which may or may not have a uniform thickness.Thus, a coating composition can be applied to the surface of the opticalelement and cured to form the coating. The term “curable,” “cure,”“cured,” or similar terms, as used in connection with a cured or curablecomposition, is intended to mean that at least a portion of thepolymerizable components that form the curable composition are at leastpartially polymerized.

The coating applied to the optical element comprises at least oneanisotropic coating layer that includes at least one anisotropicmaterial. In some examples, the anisotropic coating layer includesmultiple anisotropic materials such as two or more, three or more, orfour or more anisotropic materials. When multiple anisotropic materialsare used, the anisotropic materials can be the same or different.

As used herein, the term “anisotropic” means having at least oneproperty that differs in value when measured in at least one differentdirection and which are capable of self-assembly. Thus, “anisotropicmaterials” are materials that have at least one property that differs invalue when measured in at least one different direction and which arecapable of self-assembly. Non-limiting examples of anisotropic materialsinclude liquid crystal materials.

Liquid crystal materials, because of their structure, are generallycapable of being ordered or aligned so as to take on a generaldirection. More specifically, because liquid crystal molecules have rod-or disc-like structures, a rigid long axis, and strong dipoles, liquidcrystal molecules can be ordered or aligned by interaction with anexternal force or another structure such that the long axis of themolecules takes on an orientation that is generally parallel to a commonaxis. For example, it is possible to align the molecules of a liquidcrystal material with a magnetic field, an electric field, linearlypolarized infrared radiation, linearly polarized ultraviolet radiation,linearly polarized visible radiation, or shear forces. It is alsopossible to align liquid crystal molecules with an oriented surface.That is, liquid crystal molecules can be applied to a surface that hasbeen oriented, for example by rubbing, grooving, or photo-alignmentmethods, and subsequently aligned such that the long axis of each of theliquid crystal molecules takes on an orientation that is generallyparallel to the general direction of orientation of the surface.

Further, a mesogen is the fundamental unit of a liquid crystal material,which induces the structural order in the liquid crystal material. Themesogenic moiety of the liquid crystal material typically comprises arigid moiety which aligns with other mesogenic components of the liquidcrystal material, thereby aligning the liquid crystal molecules in onespecific direction. The rigid portion of the mesogen may consist of arigid molecular structure, such as a mono- or polycyclic ring structure,including for example, a mono- or polycyclic aromatic ring structure.

Liquid crystal mesogens that are suitable for use with present inventioninclude, but are not limited to, thermotropic liquid crystal mesogensand lyotropic liquid crystal mesogens. As used herein, a “thermotropicliquid crystal” means a liquid crystal that is ordered based ontemperature, and a “lyotripic liquid crystal” means a liquid crystalthat is ordered by the addition of solvent. Non-limiting examples ofthermotropic liquid crystal mesogens include columatic (or rod-like)liquid crystal mesogens, discotic (or disc-like) liquid crystalmesogens, and cholesteric liquid crystal mesogens. Non-limiting examplesof potential mesogens are set forth in greater detail, for example, inU.S. patent application Ser. No. 12/163,116, at paragraphs[0024]-[0047]; and include those described in Dennis, et al., “FlūssigeKristalle in Tabellen,” VEB Deutscher Verlag Fūr Grundstoffindustrie,Leipzig, Germany, 1974 and “Flūssige Kristalle in Tabellen II,” VEBDeutscher Verlag Fūr Grundstoffindustrie, Leipzig, Germany, 1984, thedisclosures of each of which are incorporated by reference herein.

The liquid crystal materials comprising one or more mesogens can includeliquid crystal polymers, liquid crystal pre-polymers, and liquid crystalmonomers. As used herein the term “pre-polymer” means partiallypolymerized materials. Further, the term “polymer” means homopolymers(e.g., prepared from a single monomer species), copolymers (e.g.,prepared from at least two monomer species), and graft polymers.

Liquid crystal monomers that are suitable for use as anisotropicmaterials include, but not limited to, mono-functional, as well asmulti-functional liquid crystal monomers. Further, the liquid crystalmonomer can be a polymerizable liquid crystal monomer, and can furtherbe a photo-polymerizable and/or thermo-polymerizable liquid crystalmonomer. As used herein, the term “photo-polymerizable” means amaterial, such as a monomer, a pre-polymer, or a polymer, that can becross-linked on exposure to actinic radiation. As used herein, the term“actinic radiation” means electromagnetic radiation and includes, forexample, and without limitation, visible and ultraviolet (UV) radiation.Further, the term “thermo-polymerizable” means a material, such as amonomer, a pre-polymer, or a polymer, that can be cross-linked onexposure to heat.

Non-limiting examples of liquid crystal monomers suitable for use asanisotropic materials include liquid crystal monomers having functionalgroups chosen from acrylates, methacrylates, allyl, allyl ethers,alkynes, amino, anhydrides, epoxides, hydroxides, isocyanates, blockedisocyanates, siloxanes, thiocyanates, thiols, urea, vinyl, vinyl ethers,and blends thereof.

Liquid crystal polymers and pre-polymers that are suitable for use asanisotropic materials include, but are not limited to, thermotropicliquid crystal polymers and pre-polymers, and lyotropic liquid crystalpolymers and pre-polymers. Further, the liquid crystal polymers andpre-polymers can be main-chain polymers and pre-polymers or side-chainpolymers and pre-polymers. In main-chain liquid crystal polymers andpre-polymers, rod- or disc-like liquid crystal mesogens are primarilylocated within the polymer backbone. In side-chain polymers andpre-polymers, the rod- or disc-like liquid crystal mesogens primarilyare located within the side chains of the polymer. Additionally, theliquid crystal polymer or pre-polymer can be photo-polymerizable.

Non-limiting examples of liquid crystal polymers and pre-polymers thatare suitable for use as anisotropic materials include, but are notlimited to, main-chain and side-chain polymers and pre-polymers havingfunctional groups chosen from acrylates, methacrylates, allyl, allylethers, alkynes, amino, anhydrides, epoxides, hydroxides, isocyanates,blocked isocyanates, siloxanes, thiocyanates, thiols, urea, vinyl, vinylethers, and blends thereof.

The anisotropic coating layer of the present invention can also includeat least one dichroic material and/or at least one photochromic-dichroicmaterial, and optionally, at least one photochromic material, andcombinations thereof. The dichroic material, and photochromic-dichroicmaterial can be aligned in the direction of the anisotropic materials.For example, a dichroic material, and/or photochromic-dichroic materialcan be incorporated into the anisotropic coating layer such that thedichroic material and/or photochromic-dichroic material are aligned inthe same direction as the surrounding anisotropic materials. Thus, thealigned anisotropic materials act as an alignment medium to align thedichroic materials and/or photochromic-dichroic materials.

As used herein the term “photochromic” means having an absorptionspectrum for at least visible radiation that varies in response to atleast actinic radiation. Further, the term “photochromic materials”includes thermally reversible photochromic materials and non-thermallyreversible photochromic materials, which are generally capable ofconverting from a first state, for example a “clear state” in at leastthe visible spectrum, to a second state, for example a “colored state”in at least the visible spectrum, in response to thermal energy and/oractinic radiation, and reverting back to the first state when notexposed to thermal energy and/or actinic radiation, provided that atleast one of the changes is in response to actinic radiation. Althoughnot limiting herein, photochromic materials used with the presentinvention can change from a clear state to a colored state in at leastthe visible spectrum, or they may change from one colored state toanother colored state in at least the visible spectrum.

Furthermore, the term “dichroic” means capable of absorbing one of twoorthogonal plane polarized components of at least transmitted radiationmore strongly than the other. One measure of how strongly the dichroicmaterial absorbs one of two orthogonal plane-polarized components is the“absorption ratio.” As used herein, the term “absorption ratio” refersto the ratio of the absorbance of radiation linearly polarized in afirst plane to the absorbance of the same wavelength radiation linearlypolarized in a plane orthogonal to the first plane, wherein the firstplane is taken as the plane with the highest absorbance.

While dichroic materials absorb one of two orthogonal plane-polarizedcomponents of transmitted radiation more strongly than the other, themolecules of the dichroic material must be suitably positioned orarranged to achieve a net polarization of transmitted radiation. Thus,when incorporated into the anisotropic coating layer, at least a portionof the at least one dichroic material can be brought into suitableposition or arrangement (i.e., ordered or aligned) such that an overallpolarization effect can be achieved.

Moreover, the term “photochromic-dichroic material” refers to materialsthat display photochromic properties and dichroic properties in responseto at least actinic radiation. For example, the anisotropic coatinglayer can include at least one photochromic-dichroic material that isadapted to reversibly switch from a first optically clear,non-polarizing state in at least the visible spectrum to a secondcolored, polarizing state in at least the visibly spectrum in responseto at least actinic radiation. As such, if the optical element is anophthalmic lens with a coating layer comprising thephotochromic-dichroic material, the lens can reversibly switch from anoptically clear, non-polarizing state when the wearer is not exposed toactinic radiation, for example, out of the sunlight, to a colored,polarizing state when the wearer is exposed to actinic radiation, forexample, from sunlight.

Non-limiting examples of organic photochromic compounds includebenzopyrans, naphthopyrans (for example naphtho[1,2-b]pyrans andnaphtho[2,1-b]pyrans) spiro-9-fluoreno[1,2-b]pyrans, phenanthropyrans,quinopyrans, and indeno-fused naphthopyrans, such as those disclosed inU.S. Pat. No. 5,645,767 at column 1, line 10 to column 12, line 57 andin U.S. Pat. No. 5,658,501 at column 1, line 64 to column 13, line 36,which disclosures are incorporated herein by reference. Additionalnon-limiting examples of organic photochromic compounds that may be usedinclude oxazines, such as benzoxazines, naphthoxazines, andspirooxazines. Other non-limiting examples of photochromic compoundsthat may be used include: fulgides and fulgimides, for example 3-furyland 3-thienyl fulgides and fulgimides, which are described in U.S. Pat.No. 4,931,220 at column 20, line 5 through column 21, line 38, whichdisclosure is incorporated herein by reference; diarylethenes, which aredescribed in U.S. Patent Application No. 2003/0174560 from paragraph[0025] to [0086], which disclosure is incorporated herein by reference;and combinations or mixtures of any of the aforementioned photochromicmaterials/compounds.

Further, suitable dichroic materials that can be used with the presentinvention include, but are not limited to, azomethines, indigoids,thioindigoids, merocyanines, indans, quinophthalonic dyes, perylenes,phthaloperines, triphenodioxazines, indoloquinoxalines,imidazo-triazines, tetrazines, azo and (poly)azo dyes, benzoquinones,naphthoquinones, anthraquinone and (poly)anthraquinones,anthrapyrimidinones, iodine and iodates, and combinations thereof.

Further still, non-limiting of photochromic-dichroic materials includethe photochromic-dichroic materials described in U.S. Patent ApplicationPublication Nos. 2005/0004361, at paragraph 27 to paragraph 158, whichdisclosure is hereby specifically incorporated herein by reference.

Other non-limiting examples of suitable photochromic materials, dichroicmaterials, and photochromic-dichroic materials can be found in U.S.patent application Ser. No. 12/329,197, filed Dec. 8, 2008, entitled“Alignment Facilities for Optical Dyes” at paragraphs [0090]-[0102] andthe references cited therein; and U.S. patent application Ser. No.12/163,180, filed Jun. 27, 2008 entitled “Formulations ComprisingMesogen Containing Compounds” at paragraphs [0064]-[0084] and thereferences cited therein, the disclosure of each of which isincorporated by reference herein. Moreover, non-limiting examples ofphotochromic materials that can be used are further described in U.S.Pat. No. 7,044,599, at column 9, line 60 to column 11, line 3, whichdisclosure is hereby specifically incorporated herein by reference.Non-limiting examples of dichroic materials that can be used are furtherdescribed in U.S. Pat. No. 7,044,599, at column 7, lines 18-56, whichdisclosure is hereby specifically incorporated herein by reference. Inaddition, other non-limiting examples of photochromic-dichroic materialsare further described in U.S. Patent Application Publication No.2005/0012998 A1, at paragraph 11 to paragraph 442, which disclosures ishereby specifically incorporated herein by reference.

The anisotropic coating layer can also include additional additives. Forexample, the anisotropic coating layer can also include mesogenicstabilizers, alignment promoters, kinetic enhancing additives,photoinitiators, thermal initiators, polymerization inhibitors,solvents, light stabilizers (such as, but not limited to, ultravioletlight absorbers and light stabilizers, such as hindered amine lightstabilizers (HALS)), heat stabilizers, mold release agents, rheologycontrol agents, leveling agents (such as, but not limited to,surfactants), free radical scavengers, adhesion promoters (such ashexanediol diacrylate and coupling agents), conventional dyes, andcombinations thereof. As used herein, “conventional dyes” refers to dyesthat provide color/tint but which not provide polarization or areversible change.

As used herein, the term “alignment promoter” means an additive that canfacilitate at least one of the rate and uniformity of the alignment of amaterial to which it is added. Non-limiting examples of alignmentpromoters include those described in U.S. Pat. No. 6,338,808 at column1, line 66 to column 35, line 23, and U.S. Patent ApplicationPublication No. 2002/0039627 at paragraphs [0036] to [0286], which arehereby specifically incorporated by reference herein.

Non-limiting examples of kinetic enhancing additives includeepoxy-containing compounds, organic polyols, and/or plasticizers. Morespecific examples of such kinetic enhancing additives are disclosed inU.S. Pat. No. 6,433,043 at column 2, line 57 to column 13, line 54, andU.S. Patent Application Publication No. 2003/0045612 at paragraphs[0012] to [0095], which are hereby specifically incorporated byreference herein.

Non-limiting examples of photoinitiators include cleavage-typephotoinitiators and abstraction-type photoinitiators. Non-limitingexamples of cleavage-type photoinitiators include acetophenones,α-aminoalkylphenones, benzoin ethers, benzoyl oximes, acylphosphineoxides and bisacylphosphine oxides or mixtures of such initiators. Acommercial example of such a photoinitiator is DAROCURE® 4265, which isavailable from Ciba Chemicals, Inc. Non-limiting examples ofabstraction-type photoinitiators include benzophenone, Michler's ketone,thioxanthone, anthraquinone, camphorquinone, fluorone, ketocoumarin ormixtures of such initiators.

Another non-limiting example of a photoinitiator includes a visiblelight photoinitiator. Non-limiting examples of suitable visible lightphotoinitiators are set forth at column 12, line 11 to column 13, line21 of U.S. Pat. No. 6,602,603, which is specifically incorporated byreference herein.

Non-limiting examples of thermal initiators include organic peroxycompounds and azobis(organonitrile) compounds. Specific non-limitingexamples of organic peroxy compounds that are useful as thermalinitiators include peroxymonocarbonate esters, such astertiarybutylperoxy isopropyl carbonate; peroxydicarbonate esters, suchas di(2-ethylhexyl)peroxydicarbonate, di(secondary butyl)peroxydicarbonate and diisopropylperoxydicarbonate; diacyperoxides, suchas 2,4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide,lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxideand p-chlorobenzoyl peroxide; peroxyesters such as t-butylperoxypivalate, t-butylperoxy octylate and t-butylperoxyisobutyrate;methylethylketone peroxide, and acetylcyclohexane sulfonyl peroxide. Inone non-limiting embodiment the thermal initiators used are those thatdo not discolor the resulting polymerizate. Non-limiting examples ofazobis(organonitrile) compounds that can be used as thermal initiatorsinclude azobis(isobutyronitrile), azobis(2,4-dimethylvaleronitrile) or amixture thereof.

Non-limiting examples of polymerization inhibitors include:nitrobenzene, 1,3,5,-trinitrobenzene, p-benzoquinone, chloranil, DPPH,FeCl3, CuCl2, oxygen, sulfur, aniline, phenol, p-dihydroxybenzene,1,2,3-trihydroxybenzene, and 2,4,6-trimethylphenol.

Non-limiting examples of solvents include those that will dissolve solidcomponents of the coating, that are compatible with the coating and theelements and substrates, and/or that can ensure uniform coverage of theexterior surface(s) to which the coating is applied. Potential solventsinclude, but are not limited to, the following: N-methyl-2-pyrrolidone,propylene glycol monomethyl ether acetate and their derivates (sold asDOWANOL® industrial solvents), acetone, amyl propionate, anisole,benzene, butyl acetate, cyclohexane, dialkyl ethers of ethylene glycol,e.g., diethylene glycol dimethyl ether and their derivates (sold asCELLOSOLVE® industrial solvents), diethylene glycol dibenzoate, dimethylsulfoxide, dimethyl formamide, dimethoxybenzene, ethyl acetate,isopropyl alcohol, methyl cyclohexanone, cyclopentanone, methyl ethylketone, methyl isobutyl ketone, methyl propionate, propylene carbonate,tetrahydrofuran, toluene, xylene, 2-methoxyethyl ether, 3-propyleneglycol methyl ether, and mixtures thereof.

As indicated, the anisotropic coating layer comprises anisotropicmaterials that can be aligned in a particular direction. In someexamples, the anisotropic materials are aligned by an alignment coatinglayer that is positioned between the optical element and the anisotropiccoating layer. Thus, the optical article of the present invention cancomprise an optical element, an alignment coating layer applied over atleast a portion of the optical element, and an anisotropic coating layerapplied over at least a portion of the alignment coating layer.

The alignment coating layer used with the present invention comprisesmaterials that can be aligned in a particular direction. For example,the alignment coating layer can comprise a rubbing material or aphoto-alignment material that can be aligned in various directionsincluding, but not limited to, a parallel orientation, ellipticalorientation, splay orientation, vertical orientation, helicalorientation, or any combination thereof.

As used herein, the term “rubbing material” means a material that can beat least partially ordered by rubbing at least a portion of a surface ofthe material with another suitably textured material. For instance, therubbing material can be rubbed with a suitably textured cloth or avelvet brush. Non-limiting examples of rubbed-orientation materialsinclude (poly)imides, (poly)siloxanes, (poly)acrylates,(poly)coumarines, and combinations thereof.

As used herein, the term “photo-alignment material” refers to a materialthat can be aligned though exposure to polarized radiation such aspolarized UV radiation. The photo-alignment material can comprisephotochemically active chromophores. As used herein, the phrase“photochemically active chromophore” includes structures or portions ofthe molecule or polymer which chemically react (such as with themselvesor with another active moiety, for example another photochemicallyactive chromophore) upon the absorption of actinic radiation. Thephotochemically active chromophore may undergo a photochemicalcis/trans-isomerization, a photochemical [2+2] cycloaddition (leading toa cross-linking of the polymer or oligomer), a photochemicaldecomposition or a photochemical rearrangement.

Non-limiting examples of suitable photochemically active chromophoresinclude, but are not limited to, dimerizable substituted orunsubstituted cinnamate or dimerizable dimerizable coumarin, cis/transisomerizable substituted or unsubstituted azo, photochemicallydecomposable polyimide, and photochemically rearrangeable substituted orunsubstituted aromatic esters. Cinnamates and coumarins may react uponexposure to actinic radiation to undergo a [2+2] cycloaddition asdescribed in “Alignment Technologies and Applications of Liquid CrystalDevices,” Kohki Takotah et al., Taylor and Francis, N.Y., 2005, pages61-63, which disclosure is incorporated herein by this reference.Non-limiting examples of suitable cinnamates may be found in U.S. Pat.No. 5,637,739 at column 6, lines 19 to 32 and U.S. Pat. No. 7,173,114 atcolumn 3, line 13 to column 5, line 2 and coumarins may be found in U.S.Pat. No. 5,231,194 at column 1, line 37 to column 3, line 50; U.S. Pat.No. 5,247,099 at column 1, line 66 to column 4 line 28; U.S. Pat. No.5,300,656 at column 1, line 13 to column 10, line 15; and U.S. Pat. No.5,342,970 at column 1, line 6 to column 7, line 34, the disclosures ofeach of which are incorporated herein by reference.

Further examples of photochemically active chromophores include: aphotoisomerizable azo compound such as Poly((n-butylmethacrylate-co-(E)-4-(phenyldiazenyl)phenyl methacrylate)-b-styrene)described in Macromol. Chem. Phys. 2009, 210, pages 1484-1492;photodegradable polyimides such asPoly(2-methyl-6-(4-(p-tolyloxy)phenyl)pyrrolo[3,4-f]isoindole-1,3,5,7(2H,6H)-tetraone),Poly(5-(2-(1,3-dioxo-2-(4-(p-tolyloxy)phenyl)isoindolin-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl)-2-methylisoindoline-1,3-dione),Poly(5-(2-(1,3-dioxo-2-(4-(2-(p-tolyl)propan-2-yl)phenyl)isoindolin-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl)-2-methylisoindoline-1,3-dione);andPoly(5-(1,1,1,3,3,3-hexafluoro-2-(2-(4-(1,1,1,3,3,3-hexafluoro-2-(p-tolyl)propan-2-yl)phenyl)-1,3-dioxoisoindolin-5-yl)propan-2-yl)-2-methylisoindoline-1,3-dione)described in Macromolecules 1994, 27, pages 832-837; a photoreactivepolyimide such as(2E,2′E)-4-(5-(1,1,1,3,3,3-hexafluoro-2-(2-methyl-1,3-dioxoisoindolin-5-yl)propan-2-yl)-1,3-dioxoisoindolin-2-yl)-4′-methyl-[1,1′-biphenyl]-3,3′-diylbis(3-phenylacrylate) described in Macromolecules 2003, 36, pages6527-6536; a photodecomposable polyimide such as7-methyl-2-(4-(4-methylbenzyl)phenyl)tetrahydro-1H-5,9-methanopyrido[3,4-d]azepine-1,3,6,8(2H,4H,7H)-tetraoneand2-methyl-5-(4-(4-(2-(4-(p-tolyloxy)phenyl)propan-2-yl)phenoxy)phenyl)hexahydrocyclobuta[1,2-c:3,4-c′]dipyrrole-13(2H,3 aH)-dione described in the The Liquid Crystal Book Series:Alignment Technologies and Application of Liquid Crystal Devices, by K.Takatoh et. al., 2005, Taylor and Francis, page 63; and aromatic esterscapable of undergoing a Photo-Fries rearrangement include:Poly(5-methacrylamidonaphthalen-1-yl methacrylate);Poly(4-methacrylamidonaphthalen-1-yl methacrylate);Poly(4-methacrylamidophenyl methacrylate);Poly(4-methacrylamidophenethyl methacrylate); andPoly(4-(2-methacrylamidoethyl)phenyl methacrylate) described inMolecular Crystal and Liquid Crystal, 2007, Vol. 479 page 121. Thedisclosures of each of the aforementioned articles and text related tophotochemically active chromophores are incorporated herein byreference.

Other non-limiting examples of suitable photo-alignment materialsinclude (co)polymeric structures comprising at least one photochemicallyactive chromophore, such as any of those previously described, and atleast one adhesion promoter group. As used herein, an “adhesionpromoter” refers to a group or structure that improves adhesion betweenthe (co)polymeric structure and a substrate, such as an optical element,to which it is coated onto or to polymeric films that are coated ontothe surface of the polymer containing the adhesion promoter. Adhesionpromoters may act by forming an at least partial attractive force on amolecular or atomic level between the (co)polymer and the substrate orsubsequent coating. Examples of attractive forces include covalentbonds, polar covalent bonds, ionic bonds, hydrogen bonds, electrostaticattractions, hydrophobic interactions, and van der Waals attractions.Within the structure of the copolymer, the attractive interactionbetween a plurality of adhesion promoter groups and the substratesurface or subsequent coating material results in an improved adhesionbetween the copolymer and the substrate surface and/or the subsequentcoating.

Non-limiting examples of suitable structures for adhesion promotergroups that can be used to form the (co)polymeric structures includehydroxy, carboxylic acid, anhydride, isocyanato, blocked isocyanato,thioisocyanato, blocked thioisocyanato, amino, thio, organofunctionalsilane, organofunctional titanate, organofunctional zirconate, andepoxy, wherein each organofunctional group is independently selectedfrom vinyl, allyl, vinyl-functional hydrocarbon radicals,epoxy-functional hydrocarbon radicals, allyl-functional hydrocarbonradicals, acryloyl-functional hydrocarbon radicals,methacryloyl-functional hydrocarbon radicals, styryl-functionalhydrocarbon radicals, mercapto-functional hydrocarbon radicals orcombinations of such organofunctional groups, said hydrocarbon radicalsbeing selected from C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C1-C20alkoxy, C1-C20 alkyl(C1-C20)alkoxy, C1-C20 alkoxy(C1-C20)alkyl, aryl,heteroaryl, and combinations of such hydrocarbon radicals; provided thatwhen the adhesion promoter group is hydroxy or carboxylic acid, the(co)polymer further comprises at least one other adhesion promotergroup; such as, but not limited to those promoters disclosed in U.S.Pat. No. 6,025,026 at column 6, line 5 to column 8, line 65; U.S. Pat.No. 6,150,430 at column 2, line 59 to column 5, line 44; and U.S. Pat.No. 7,410,691 at column 6, line 4 to column 8, line 19; whichdisclosures are incorporated herein by reference. As used herein, theterm “blocked” when used in reference to isocyanato or thioisocyanatogroups refers to a structure where the isocyanato or thioisocyanatogroup has been reversibly reacted with a group to protect the isocyanatoor thioisocyanato group from reacting until the blocking group isremoved. Generally, compounds used to block isocyanato or thioisocyanatogroups may be organic compounds that have active hydrogen atoms, forexample, but not limited to, volatile alcohols, epsilon-caprolactam orketoxime compounds. Non-limiting examples of blocking groups includeamines, hydrooxamic esters, substituted or unsubstituted pyrazol groups,phenols, cresol, nonylphenol, caprolactam, triazole, imidazoline, oxime,formate and diacetone, including those described in X. Tassel et al., “ANew Blocking Agent of Isocyanates” European Polymer Journal, 2000, 36,1745-1751 and Z. W. Wicks Jr., Progress in Organic Coatings, 1975, 3,73-99, which disclosures are incorporated herein by this reference.

Specific non-limiting examples of such (co)polymeric structures aredescribed in U.S. Patent Application Publication No. 2011/0135850 atparagraphs [0031]-[0053] and [0091]-[0102], the disclosure of which isincorporated by reference herein. It is appreciated that the alignmentcoating layer can include any of the additional additives previouslydescribed with reference to the anisotropic coating layer.

As previously noted, an anisotropic coating layer, and, optionally, analignment coating layer, such as previously described, can be appliedover at least a portion of a surface of an optical element. Theanisotropic layer or the alignment coating layer can be applied directlyover at least a portion of the surface of the optical element. When analignment coating layer is formed over at least a portion of the surfaceof the optical element, an anisotropic coating layer can be applieddirectly over the alignment coating layer such that the anisotropicmaterials and additional materials such as dichroic, photochromic, andphotochromic-dichroic materials for example, are aligned by thealignment coating layer. As used herein, the phrase “applied directlyover” means that a coating layer is formed over the surface of anoptical element or over the surface of another coating layer without anyother component positioned in between such as another coating layer.

Generally the thickness of at least the anisotropic coating layer can beany thickness necessary to achieve the desired thickness for the opticalarticle of manufacture. For example, the thickness of at least theanisotropic coating layer can be from 0.1 microns to 1 millimeter, from5 microns to 50 microns, or from 10 microns to 30 microns. The alignmentcoating layer can also have the same thickness as the anisotropiccoating layer.

Additional coating layers can also be used with the anisotropic andalignment coating layers. That is, one or more additional layers may beapplied onto the surface of the optical element, onto the surface of theanisotropic coating layer, and/or onto the surface of the alignmentcoating layer. Non-limiting examples of additional coating layersinclude a separate tie layer, primer layer, abrasion resistant coatinglayer, hard coating layer, protective coating layer, reflective coatinglayer, photochromic coating layer, dichroic coating layer,photochromic-dichroic coating layer, anti-reflective coating layer,linearly polarizing coating layer, circularly polarizing coating layer,elliptically polarizing coating layer, transitional coating layer,compatibilizing coating layer, functional organic coating layer,retarder layer, or combinations thereof. A description and non-limitingexamples of at least some of these additional layers is described inU.S. Patent Application Publication No. 2011/0135850 at paragraphs[0060]-[0064], the disclosure of which is incorporated by referenceherein.

Moreover, the anisotropic coating layer, and optionally the alignmentcoating layer, can be applied to an optical element to form an opticalarticle with one or more light influencing properties. As used herein,the term “light influencing property” refers to the capability of anoptical article to exhibit one or more optical properties when lightcontacts or traverses through the optical article. Non-limiting examplesof light influencing properties include color/tint, polarization,photochromic and/or photochromic-dichroic reversible changes, orcombinations thereof. The anisotropic coating layer, and optionally thealignment coating layer, can be applied over an optical element to formmultiple light influencing zones with different light influencingproperties. Further, the anisotropic coating layer, and optionally thealignment coating layer, can be applied over an optical element in apredetermined pattern to form a light-influencing zone in thepredetermined pattern.

In some examples, an anisotropic coating layer, and optionally analignment coating layer, are applied over an optical element to form atleast one light influencing zone with at least one uniform or gradientlight influencing property. For instance, an anisotropic coating layer,and optionally an alignment coating layer, are applied over an opticalelement to form at least one light influencing zone with uniformpolarization or gradient polarization. As used herein, “uniformpolarization” refers to a constant magnitude or degree of polarizationthroughout the at least one light influencing zone, and “gradientpolarization” refers to an increase or decrease in the magnitude ordegree of polarization throughout the at least one light influencingzone. To provide uniform polarization, the anisotropic coating layer canhave the same amount of aligned dichroic materials and/or the sameamount of aligned photochromic-dichroic materials throughout the atleast one light influencing zone. Further, to provide gradientpolarization, the anisotropic coating layer can have different amountsof aligned dichroic materials and/or different amounts of alignedphotochromic-dichroic materials throughout the at least one lightinfluencing zone. The amount of aligned dichroic and/orphotochromic-dichroic materials can be varied by incorporating differentquantities of dichroic and/or photochromic-dichroic materials throughoutthe at least one light influencing zone, or by incorporating similarquantities of dichroic and/or photochromic-dichroic materials but thenaligning different amounts of the dichroic and/or photochromic-dichroicmaterials throughout the at least one light influencing zone.

The anisotropic coating layer, and optionally an alignment coatinglayer, can also be applied over an optical element to form at least onelight influencing zone with uniform color/tint or gradient color/tint.As used herein, “uniform color/tint” refers to a constant magnitude ordegree of color/tint throughout the at least one light influencing zone,and “gradient color/tint” refers to an increase or decrease in themagnitude or degree of color/tint throughout the at least one lightinfluencing zone. To provide uniform color/tint, the anisotropic coatinglayer can have the same amount of dichroic materials, photochromicmaterials, photochromic-dichroic materials, and/or conventional dyesthroughout the at least one light influencing zone. Further, to providegradient color/tint, the anisotropic coating layer can have differentamounts of dichroic materials, photochromic materials,photochromic-dichroic materials, and/or conventional dyes throughout theat least one light influencing zone.

The anisotropic coating layer, and optionally an alignment coatinglayer, can also be applied over an optical element to form at least onelight influencing zone with a uniform photochromic and/orphotochromic-dichroic reversible change or a gradient photochromicand/or photochromic-dichroic reversible change. As used herein, “uniformphotochromic and/or photochromic-dichroic reversible change” refers to aconstant magnitude or degree in a color/tint and/or polarization changethroughout the at least one light influencing zone when exposed to atleast actinic radiation, and “gradient photochromic and/orphotochromic-dichroic reversible change” refers to an increase ordecrease in the magnitude or degree of a color/tint and/or polarizationchange throughout the at least one light influencing zone when exposedto at least actinic radiation. To provide a uniform photochromic and/orphotochromic-dichroic reversible change, the anisotropic coating layercan have the same amount of photochromic materials and/orphotochromic-dichroic materials throughout the at least one lightinfluencing zone. Further, to provide a gradient photochromic and/orphotochromic-dichroic reversible change, the anisotropic coating layercan have different amounts of photochromic materials and/orphotochromic-dichroic materials throughout the at least one lightinfluencing zone.

As will be appreciated, the use of photochromic materials andphotochromic-dichroic materials to provide uniform or gradientpolarization and/or color/tint will also provide a uniform or gradientphotochromic and/or photochromic-dichroic reversible change. Thus, byusing photochromic materials and/or photochromic-dichroic materials, alight influencing zone with at last two different light influencingproperties can be formed. It is also appreciated that the anisotropiccoating layer, and optionally an alignment coating layer, can be appliedover an optical element to form one or more light influencing zones thatindependently comprise any combination of uniform or gradient lightinfluencing properties.

As indicated, the optical article can comprise two or more lightinfluencing zones with different light influencing properties. As such,the optical article of the present invention can comprise two or morelight influencing zones with different polarization properties,different color/tint, different photochromic and/orphotochromic-dichroic reversible changes, or any combination thereof.

In some examples, the optical article comprises at least two lightinfluencing zones with different polarization properties. For instance,the optical article can include: (i) at least a first light influencingzone with a polarization alignment that is different than thepolarization alignment of at least a second light influencing zone; (ii)at least a first light influencing zone with a greater or lessermagnitude/degree of polarization than the polarization of at least asecond light influencing zone; (iii) at least a first light influencingzone with uniform polarization and at least a second light influencingzone with no polarization; (iv) at least a first light influencing zonewith a gradient polarization and at least a second light influencingzone with no polarization; (v) at least a first light influencing zonewith a gradient polarization and at least a second light influencingzone with uniform polarization; (vi) at least a first light influencingzone with a first gradient polarization and at least a second lightinfluencing zone with a second gradient polarization that is differentthan the first gradient polarization such as, for example, a differentdegree/magnitude of polarization change, a different polarizationalignment, or a different directional change in polarizationmagnitude/degree; or (vii) any combinations thereof.

Moreover, the optical article can also comprise at least two lightinfluencing zones with different photochromic and/orphotochromic-dichroic reversible changes. For example, the opticalarticle can include: (i) at least a first light influencing zone thatcomprises photochromic materials and at least a second light influencingzone with no photochromic materials; (ii) at least a first lightinfluencing zone that comprises photochromic-dichroic materials and atleast a second light influencing zone with no photochromic-dichroicmaterials; (iii) at least a first light influencing zone that comprisesa gradient photochromic reversible change and at least a second lightinfluencing zone with a uniform photochromic reversible change; (iv) atleast a first light influencing zone that comprises a gradientphotochromic-dichroic reversible change and at least a second lightinfluencing zone with a uniform photochromic-dichroic reversible change;or (v) any combination thereof.

The optical article can further comprise at least two light influencingzones with different color/tint properties. For example, the opticalarticle can include: (i) at least a first light influencing zone with agreater or lesser magnitude/degree of color/tint than the color/tint ofat least a second light influencing zone; (ii) at least a first lightinfluencing zone with a different hue of color/tint than the hue ofcolor/tint of at least a second light influencing zone; (iii) at least afirst light influencing zone with uniform color/tint and at least asecond light influencing zone with no color/tint; (iv) at least a firstlight influencing zone with a gradient color/tint and at least a secondlight influencing zone with no color/tint; (v) at least a first lightinfluencing zone with a gradient color/tint and at least a second lightinfluencing zone with uniform color/tint; (vi) at least a first lightinfluencing zone with a first gradient color/tint and at least a secondlight influencing zone with a second gradient color/tint that isdifferent than the first gradient color/tint such as, for example, adifferent magnitude of color/tint change or a different spatialdirectional change in color/tint; or (vii) any combinations thereof.

An optical article can be formed with any combination of the previouslydescribed non-limiting light influencing zones and properties. Further,the optical article can comprise any desired number of light influencingzones including, but not limited to, two or more, three or more, or fouror more light influencing zones. The number and types of lightinfluencing zones can be selected based on the desired use of theoptical article. For example, an optical article that is used as anophthalmic lens can have a dark, strongly polarizing first zone thatsufficiently blocks sunlight and selectively reduces glare, and alighter, lesser polarizing second zone for reading and viewing digitaldisplays in an automobile, airplane, or boat. Specific non-limitingexamples of ophthalmic lenses with one or more light influencing zonesare further illustrated in FIGS. 1-5.

As shown in FIG. 1, an anisotropic coating layer, and optionally analignment coating layer, can be applied over an ophthalmic lens 10having a top surface 12 formed between an upper edge 14, a lower edge16, and two lateral edges 18 and 20 extending from the upper edge 14 tothe lower edge 16. As shown in FIG. 1, the anisotropic coating layerprovides uniform color/tint and gradient polarization over the entiretop surface 12 of the ophthalmic lens 10 such that the magnitude ordegree of polarization decreases from the upper edge 14 to the loweredge 16 and the magnitude or degree of color/tint remains same from theupper edge 14 to the lower edge 16.

Referring to FIG. 2, an anisotropic coating layer, and optionally analignment coating layer, are applied over an ophthalmic lens 24 having atop surface 26 formed between an upper edge 28, a lower edge 30, and twolateral edges 32 and 34 extending from the upper edge 28 to the loweredge 30. As further shown in FIG. 2, a first light influencing zone 36with high degree of horizontal polarization is formed over an upperportion of the top surface 26 of the lens 24 and a second lightinfluencing zone 38 with no polarization is formed over a lower portionof the top surface 26 of the lens 24.

As shown in FIG. 3, an anisotropic coating layer, and optionally analignment coating layer, are applied over an ophthalmic lens 40 having atop surface 42 formed between an upper edge 44, a lower edge 46, and twolateral edges 48 and 50 extending from the upper edge 44 to the loweredge 46. As further shown in FIG. 3, first light influencing zones 52with vertical polarization are formed over the side portions of the topsurface 42 adjacent to the lateral edges 48 and 50, and a second lightinfluencing zone 54 with horizontal polarization is formed over acentral portion of the top surface 26 of the lens 24 between the upperedge 44, the lower edge 46, and the first light influencing zones 52.

FIG. 4 illustrates an anisotropic coating layer, and optionally analignment coating layer, applied over an ophthalmic lens 58 having a topsurface 60 formed between an upper edge 62, a lower edge 64, and twolateral edges 66 and 68 extending from the upper edge 62 to the loweredge 64. As shown in FIG. 4, first light influencing zones 70 withvertical polarization are formed over the side portions of the topsurface 60 adjacent to the lateral edges 66 and 68, a second lightinfluencing zone 72 with horizontal polarization is formed over an upperportion of the top surface 60 of the lens 58 between the first lightinfluencing zones 70, and a third light influencing zone 74 with nopolarization is formed over a lower portion of the top surface 60 of thelens 58 between the first light influencing zones 70.

FIG. 5 illustrates an anisotropic coating layer, and optionally analignment coating layer, applied over an ophthalmic lens 76 having a topsurface 78 formed between an upper edge 80, a lower edge 82, and twolateral edges 84 and 86 extending from the upper edge 80 to the loweredge 82. As shown in FIG. 5, a first light influencing zone 88 withgradient polarization and gradient tint is formed over an upper portionof the top surface 78 of the lens 76 and a second light influencing zone90 with gradient polarization and gradient tint is formed over a lowerportion of the top surface 78 of the lens 76. Further, the first lightinfluencing zone 88 shown in FIG. 5 has a greater degree of polarizationand tint than the second light influencing zone 90. This arrangement canprovide a gradual change in polarization and tint from the upper edge 80to the bottom edge 82 with two different light influencing zones.

As previously indicated, the present invention is also directed to amethod of preparing optical articles including, but not limited to, anyof the optical articles previously described. The optical articles canbe prepared by forming an anisotropic coating layer and, optionally, analignment coating layer over an optical element. A variety of methodscan be used to form these coating layers including, but not limited to,imbibing, overmolding, spin coating, spray coating, spray and spincoating, curtain coating, flow coating, dip coating, injection molding,casting, roll coating, spread coating, casting-coating, reverseroll-coating, transfer roll-coating, kiss/squeeze coating, gravureroll-coating, slot-die coating, blade coating, knife coating, rod/barcoating and wire coating, inkjet printing, and combinations of any ofthese methods. Various coating methods suitable for use in certainnon-limiting embodiments of the present disclosure are also described in“Coating Processes”, Kirk-Othmer Encyclopedia of Chemical Technology,Volume 7, pp 1-35, 2004. Non-limiting methods of imbibition aredescribed in U.S. Pat. No. 6,433,043 at column 1, line 31 to column 13,line 54. The disclosure of each of these references is incorporated intheir entirety by these references.

Generally, the optical articles are prepared by applying at least oneanisotropic material and at least one dichroic material and/or at leastone photochromic-dichroic material to form one or more light influencingzones as previously described. Optionally, at least one photochromicmaterial and/or at least one conventional dye can also be applied.Typically, at some of these materials are applied to the optical elementwith other additives, such as the additives previously described, in oneor more coating compositions. For example, a coating compositionscomprising at least one anisotropic material can be applied to theoptical element, aligned in one or more directions, and then cured toform at least one anisotropic coating layer.

Further, an anisotropic coating composition comprising at least oneanisotropic material can also include at least one dichroic materialand/or at least one photochromic-dichroic material, and, optionally, atleast one photochromic material and/or at least one conventional dye.Thus, the anisotropic material, at least one dichroic material and/or atleast one photochromic-dichroic material, and, optionally, at least onephotochromic material and/or at least one conventional dye can beapplied to the optical element simultaneously, aligned, and then cured.Alternatively, the at least one dichroic material, at least onephotochromic-dichroic material, and, optionally, at least onephotochromic material and at least one conventional dye can be diffusedinto an aligned and cured anisotropic coating layer through imbibition.As such, the at least one dichroic material, at least onephotochromic-dichroic material, and, optionally, at least onephotochromic material and at least one conventional dye can beincorporated into an aligned and cured anisotropic coating layer at alater time.

As used herein, the term “imbibition” refers to the process of diffusingor permeating the dichroic material, photochromic-dichroic material,photochromic material, and/or conventional dye into a host material orcoating, solvent assisted transfer of such materials into a porouspolymer, vapor phase transfer, heat transfer, and the like. Imbibitionof dyes into the anisotropic coating layer can include a step ofapplying, onto at least a portion of the anisotropic coating layer, acomposition comprising one or more imbibition resins and at least onedichroic material, photochromic-dichroic material, photochromicmaterial, and/or conventional dye. The composition is then heated suchthat the dyes are diffused or imbibed into the anisotropic coatinglayer. The remaining imbibing resins and other residual materials can bewashed from the surface of the anisotropic coating layer. The imbibingof dyes into the anisotropic coating layer can also utilize a dyetransfer substrate. As used herein, a “dye transfer substrate” refers toa component that can absorb and release dyes under certain conditions.The dye transfer substrate can absorb and release dichroic materials,photochromic materials, photochromic-dichroic materials, and/orconventional dyes into the anisotropic coating layer. The dye transfersubstrate can release the dye materials under heat and/or pressure.

As previously noted, the at least the anisotropic materials are alignedafter applying the anisotropic coating composition. The anisotropicmaterials can be aligned by heating the anisotropic coating composition.Generally, the anisotropic coating composition is heated without curingthe composition. For instance, the anisotropic coating composition istypically heated at a temperature from 10° C. to 90° C. and for a timeperiod ranging from 10 minutes to 200 minutes. The anisotropic coatingcomposition can then be cured using a variety of art recognizedtechniques including, but limiting to, actinic radiation treatment, heattreatment such as by heating the composition at a temperature higherthan the aligning temperature, and combinations thereof.

In some examples, the anisotropic materials are aligned by thedirectional information in an alignment coating layer that is positionedbetween the optical element and the anisotropic coating layer. Thus, themethod of preparing the optical articles of the present invention caninclude a step of forming an alignment coating layer over at least aportion of a surface of the optical element before applying theanisotropic coating composition. The anisotropic coating composition canthen be applied over at least a portion of the alignment coating layerand cured.

The alignment coating layer can be formed by applying an alignmentcoating composition comprising an alignment material and then at leastpartially aligning the alignment material in any desired direction(s).As used herein, the phrase “at least partially” when used in referenceto the degree of alignment of alignable materials in a coating layermeans that from 10% to 100% of the alignable elements of the materialare aligned. The alignable elements of the material can also displayfrom 25% to 100% alignment, from 50% to 100% alignment, or 100%alignment. Suitable methods for at least partially aligning thealignment materials include, but are not limited to, exposing at least aportion of the composition to a magnetic field, exposing at least aportion of the composition to a shear force, exposing at least a portionof the composition to an electric field, exposing at least a portion ofthe composition to plane-polarized ultraviolet radiation, exposing atleast a portion of the composition to infrared radiation, drying atleast a portion of the composition, etching at least a portion of thecomposition, rubbing at least a portion of the composition, andcombinations thereof. Suitable alignment methods for layers are alsodescribed in detail in U.S. Pat. No. 7,097,303, at column 27, line 17 tocolumn 28, line 45, which disclosure is incorporated by referenceherein.

In some examples, an alignment coating composition comprising aphoto-alignment material, such as any of those previously described, isapplied over at least a portion of a surface of an optical element andaligned in any desired direction through exposure to polarizingelectromagnetic radiation. The anisotropic coating composition is thenapplied over at least a portion of the alignment coating layer, and atleast a portion of the anisotropic materials are aligned in thedirection of the photo-alignment material. The anisotropic coatingcomposition is then cured to form an anisotropic coating layer. If theanisotropic coating composition did not include any dye materials, thenat least one dichroic material and/or at least one photochromic-dichroicmaterial, and, optionally, at least one photochromic material andconventional dye are applied and diffused into the already formedanisotropic coating layer.

The methods described herein are also be used to form an optical articlewith one or multiple light influencing zones. These light influencingzones can be formed by the anisotropic coating layer, the alignmentcoating layer, or a combination thereof. It is appreciated that themethods of the present invention can be used to form any of thepreviously described light influencing zones.

To form the light influencing zones with the anisotropic coating layer,various methods such as spraying, spin coating, and any of the othernon-limiting techniques previously described can be used to apply one ormore coating compositions with anisotropic materials and different typesand/or amounts of dye materials (i.e. dichroic material,photochromic-dichroic material, photochromic material, and/orconventional dye). For example, a first coating composition comprisinganisotropic materials and at least one dichroic material can be appliedover a first region of an alignment coating layer, and a second coatingcomposition comprising anisotropic materials and at least onephotochromic material can be applied over a second region of analignment coating layer. The anisotropic coating compositions can thenbe aligned and cured to form a single anisotropic coating layer with afirst light influencing zone that exhibits a fixed color/tint and fixedpolarization, and a second light influencing zone that exhibits areversible color change and no polarization. Imbibition methods can alsobe used to form an anisotropic coating layer with different lightinfluencing zones. For instance, different amounts and/or types of dyesmaterials can be diffused into different regions of an already curedanisotropic coating layer such that multiple light influencing zones areformed.

While multiple anisotropic coating compositions can be used to providedifferent light influencing zones, the multiple anisotropic coatingcompositions are applied and cured to form a single and continuousanisotropic coating layer over the optical element and/or over thealignment coating layer. The single and continuous anisotropic coatinglayer provides a coating with multiple light influencing properties thathave a continuous transition over the optical article.

Further, the alignment coating layer can also be used to form lightinfluencing zones. In some examples, light influencing zones are formedby selectively exposing different regions of a photo-alignment coatingcomposition to polarized electromagnetic radiation in differentdirections. For instance, an alignment coating composition comprisingphoto-alignment materials can be applied to an optical element, and atleast a first portion of the alignment coating composition can beexposed to polarized UV radiation in a first direction while at least asecond portion of the alignment coating composition can be exposed topolarized UV radiation in a second direction that is different from thefirst direction. An anisotropic coating layer comprising dichroicmaterials and/or photochromic-dichroic materials, and, optionally,photochromic materials and conventional dyes is then formed over thealignment coating layer. The dichroic materials and/orphotochromic-dichroic materials applied over the first portion of thealignment coating layer will align in the first direction to form afirst light influencing zone, and the dichroic materials and/orphotochromic-dichroic materials applied over the second portion of thealignment coating layer will align in the second direction to form asecond light influencing zone. Those skilled in the art will appreciatethat this process can be used to form multiple light influencing zones.

With reference to photo-alignment coating layers, a masking method canbe used to selectively align different regions of the photo-alignmentcoating composition. As used herein, with reference to aligning regionsof a photo-alignment coating layer, “masking” refers to the use of acomponent that blocks polarized UV radiation. The component used toblock different regions of the photo-alignment coating compositionincludes, but is not limited to, positive and negative UV blockingsheets. Further, a single masking step or multiple masking steps can beused to selectively align different regions of the photo-alignmentcoating composition. With reference to a single masking step, a maskingsheet that blocks polarized UV radiation can be applied over a firstregion of the photo-alignment coating composition. After applying themasking sheet, the photo-alignment coating composition is exposed topolarized UV radiation in a first direction. The masking sheet is thenremoved and the entire photo-alignment coating composition is exposed topolarized UV radiation in a second direction that is different than thefirst direction. The resulting photo-alignment coating layer will haveat least a first region with photo-alignment materials aligned in thefirst direction and at least a second region with photo-alignmentmaterials aligned in the second direction.

Alternatively, with reference to multiple masking steps, a first maskingsheet that blocks polarized UV radiation can be applied over a firstregion of the photo-alignment coating composition. After applying thefirst masking sheet, the photo-alignment coating composition is exposedto polarized UV radiation in a first direction. The first masking sheetis then removed and a second masking sheet is applied over a secondregion of the photo-alignment coating composition. The photo-alignmentcoating composition is then exposed to polarized UV radiation in asecond direction that is different the first direction. The resultingphoto-alignment coating layer will have at least a first region withphoto-alignment materials aligned in the first direction and at least asecond region with photo-alignment materials aligned in the seconddirection.

The masking method can also be used to form an alignment coating layerwith gradient polarization. For example, gradient polarization can beformed by using a masking sheet that allows gradient amounts ofpolarized UV radiation into the alignment coating composition such thatincreasing amounts of photo-alignment materials align from one end ofthe coating layer to the other. This technique can also be used toprovide gradient polarization along at least two different polarizingdirections by subsequently using a second gradient masking sheet thatblocks polarized radiation in a different polarizing direction. It isappreciated that the dichroic materials and/or photochromic-dichroicmaterials will align to from the gradient polarization based on thegradient amounts of aligned anisotropic materials.

As indicated, an inkjet printer can also be used to form the opticalarticles of the present invention. As shown in FIG. 6, the inkjetprinter 100 can include a printing head 102 that is fluidly connected toa source(s) containing anisotropic materials 104, dichroic materials106, photochromic materials 108, photochromic-dichroic materials 110,and/or conventional dyes 112 that do not polarize or reversibly changecolor. During operation, the inkjet printing head 100 can scan theinkjet printing header 102 over the optical element 103 and applyanisotropic materials 104, dichroic materials 106, photochromicmaterials 108, photochromic-dichroic materials 110, and/or conventionaldyes 112 onto an optical element 103. The inkjet printer can apply theanisotropic materials 104, dichroic materials 106, photochromicmaterials 108, photochromic-dichroic materials 110, and/or conventionaldyes 112 simultaneously. Alternatively, the inkjet printer 100 can applythe dichroic materials 106, photochromic materials 108,photochromic-dichroic materials 110, and/or conventional dyes 112 afterapplying the anisotropic materials 102. As will be recognized by oneskilled in the art, the anisotropic materials 104, dichroic materials106, photochromic materials 108, photochromic-dichroic materials 110,and/or conventional dyes 112 are typically applied with additionaladditives in a coating composition as previously described.

The inkjet printing process described herein allows a user to applydifferent types and/or amounts of dye materials such that differentlight influencing zones can be formed over different regions of theoptical article. As such, the inkjet printer 100 can be used to applydifferent amounts and/or types of dichroic materials 106, photochromicmaterials 108, photochromic-dichroic materials 110, and/or conventionaldyes 112 to an optical element 103 to form an optical article with oneor more light influencing zones including, but not limited to, any ofthe light influencing zones previously described.

The inkjet printer can also be used to form an anisotropic coating layerthat does not include any dye materials so that the dye materials can beincorporated at a later time. For example, the inkjet printer 100 can beused to apply an anisotropic coating layer with anisotropic materials104 onto an optical element 103. Then, at a later time, dichroicmaterials, photochromic materials, photochromic-dichroic materials,and/or conventional dyes can be incorporated through an imbibitionmethod.

In some examples, an optical element 103 is coated with an alignmentcoating layer, such as through a spin coating method for example. Theentire alignment coating layer can be aligned in one direction or it canhave different regions aligned in different directions as previouslydescribed. The inkjet printer 100 can then apply the anisotropic coatinglayer comprising anisotropic materials 104 and various dyes to form anoptical article with one or more light influencing zones. It has beenfound that the inkjet printer 100 can accurately and precisely applyvarious types of dye materials to provide an optical article withmultiple light influencing zones at any desired region of the article.

The optical article with multiple light influencing zones can also beformed by applying two or more anisotropic coating compositions with atleast one anisotropic material and one or more dichroic materials and/orphotochromic-dichroic materials followed by a spinning process. Forexample, the two or more anisotropic coating compositions can be appliedby any of the previously described coating processes, such as spraycoating for example, and then spun for a particular amount of time andat a certain speed (i.e., revolutions per minute (rpms)) such that thecoating compositions form one continuous compositional layer over anoptical element. Further, a portion of any of the anisotropic coatingcompositions may or may not overlap with another anisotropic coatingcomposition when applied to the optical element. In some examples,overlapping portions of separate anisotropic coating compositions can bespun to provide a gradient such as any of the gradients previouslydescribed. The spinning process can also be controlled to prevent anysubstantial overlap of different coating compositions. After spinning,the continuous compositional layer can be cured to form the anisotropiccoating layer with multiple light influencing zones.

Moreover, in some examples, an optical article with one or more lightinfluencing zones is prepared by imbibition of dyes such as through adip dying process or with the use of a dye transfer substrate. Thedifferent steps of this process can be performed at different points intime by different individuals, entities, and the like. It will beappreciated that optical articles, such as those previously described,can be produced with this process. For example, referring to FIG. 7, anoptical article 200 with one or more light influencing zones, asdescribed above, can be produced through an imbibition process, yieldingthe optical article 200 with one more light influencing zones having acontinuous gradient tint and gradient polarization. However, thegradient tint and gradient polarization of the optical article 200 canalso have a non-continuous gradient (i.e. a step gradient). Aspreviously indicated, the optical article 200 can include an opticalelement including, but not limited to an optical lens, an ophthalmiclens, an optical filter, a window, a visor, a mirror, a display, and thelike. In addition, the optical element can comprise at least one majorsurface, and at least one alignment zone can be located over at least aportion of the one major surface. The major surface can be a curvedsurface or a non-curved surface.

As shown in FIG. 7, the gradient tint and gradient polarization of theoptical article 200 can extend over an entire surface of the opticalarticle 200. For instance, in FIG. 7, the tint gradient extends from thetop of the optical article 200, where the tint is darkest, to the bottomof the optical article 200, where the tint is lightest, or where no tintis present. FIG. 7 also shows a gradient polarization over the entiresurface of the optical article 200 with the polarization gradientextending from the top of the optical article 200, where there is themost polarization, to the bottom of the optical article, where there isthe least polarization, or where there is no polarization. However, inother examples, the tint gradient and the polarization gradient canextend over only part of the surface of the optical article 200.

FIG. 7 also shows an end of the optical article 200 having the darkesttint corresponding to an end of the optical article 200 having the mostpolarization, and the end of the optical article 200 having the lightestor no tint corresponding to the end of the optical article having theleast polarization or no polarization. Therefore, the gradients of tintand polarization in FIG. 7 decrease in tint/polarization in the samedirection. However, in other examples, the end of the optical article200 having the most polarization may be different than the end of theoptical article 200 having the darkest tint, and the direction of thetint and polarization gradients along the optical article 200 can bedifferent as well.

FIGS. 8A-9E are block diagrams showing exemplary methods for making anoptical article having a gradient tint and a gradient polarization.

Referring to FIGS. 8A-8C, a producer of optical articles can makeoptical articles having a gradient tint and gradient polarization. Aproducer can be any maker of optical articles, and in some examplesinclude manufacturers of lenses, suppliers of lenses, and ophthalmiclaboratories. As shown in FIG. 8A, in one exemplary process 210, theproducer provides an optical element comprising at least an anisotropiccoating layer having at least one alignment zone 212 orientated in aparticular direction and contacts a dye composition with the anisotropiccoating layer 214 of the optical element to diffuse at least a portionof the dye composition into the anisotropic coating layer at apredetermined concentration gradient along at least a portion of theanisotropic coating layer to provide the gradient tint and the gradientpolarization. In another exemplary process 220, before the step ofproviding an optical element comprising at least an anisotropic coatinglayer having at least one alignment zone 212, the anisotropic coatinglayer having at least one alignment zone is formed on the opticalelement 222. In another process 230, before the step of providing anoptical element comprising at least an anisotropic coating layer havingat least one alignment zone 212, an optical element is provided inprefabricated form 232.

Referring to FIGS. 8D and 8E, a producer can make optical articleshaving a gradient tint and gradient polarization. In the exemplaryprocess, 240 shown in FIG. 8D, the producer obtains at least one desiredproduct property from a consumer 242. The producer also obtains anoptical element and dye composition from a single commercial source 244.An optical element comprising at least an anisotropic coating layerhaving at least one alignment zone is provided 212. A dye composition isthen applied to the anisotropic coating layer by dipping the opticalarticle into a dye solution comprising the dye composition 246. Theoptical article is then withdrawn from the dye solution at a ratesufficient to provide a predetermined concentration gradient 248. Inanother exemplary process 250, the producer obtains at least one desiredproduct property from a consumer 242. The producer also obtains anoptical element and dye composition from a single commercial source 244.The optical element comprises at least an anisotropic coating layerhaving at least one alignment zone 212. The anisotropic coating layer ofthe optical article is then contacted with a dye transfer substratecomprising a gradient layer of the dye composition 252. Heat is thenapplied to the dye transfer substrate to cause at least a portion of thedye composition to diffuse into the anisotropic coating layer at thepredetermined concentration gradient 254.

Referring to FIGS. 9A-9C, an optical article having a gradient tint andgradient polarization can be made. In one process 310, the opticalarticle can be made by contacting one or more dye compositions with anoptical element having a continuous anisotropic coating layer includingat least one alignment zone 312. In another exemplary process 320, analignment coating composition is applied over the optical element and afirst alignment region is formed over at least a portion of the opticalelement 322. An anisotropic coating composition comprising ananisotropic material is then applied over the first alignment region,aligned to form a first alignment zone, and then cured to form acontinuous anisotropic coating layer 324. The optical element having acontinuous anisotropic coating layer including at least one alignmentzone can then be contacted by one or more dye compositions 312. Inanother process 330, an alignment coating composition is applied overthe optical element and a first alignment region is formed over at leasta portion of the optical element 322. A second alignment region of thealignment coating composition is then formed over at least a secondportion of the optical element 332. An anisotropic coating compositioncomprising an anisotropic material is applied over the first alignmentregion, aligned to form a first alignment zone, and then cured to form acontinuous anisotropic coating layer 324. A second anisotropic coatingcomposition is next applied over the second alignment region to form thesecond alignment zone 334. The optical element having a continuouscoating including at least two alignment zone can then be contacted byone or more dye compositions 312.

Referring to FIGS. 9D-9E, an optical article having a gradient tint andgradient polarization can be made. According to one exemplary process340, an alignment coating composition can be applied over at least aportion of an optical element 342. A first portion of the alignmentcoating composition can be exposed to a first polarized radiation havinga first polarizing direction to form the first alignment region in thealignment coating layer 344. A second portion of the alignment coatingcomposition can be exposed to a second polarized radiation having asecond polarizing direction to form the second alignment region in thealignment layer 346. An anisotropic coating composition comprising ananisotropic material can be applied over the first alignment region,aligned, and cured to form a first alignment zone 324, and a secondanisotropic coating composition can be applied over the second alignmentregion, aligned, and cured to form a second alignment zone 334. The dyecomposition can contact the optical element by dipping the opticalelement into a dye solution comprising dye compositions 348. The opticalelement can then be withdrawn from the dye solution to provide thepredetermined concentration gradient. In a second exemplary process 350,the dye composition contacts the optical element by contacting thecoating with a dye transfer substrate comprising a gradient layer of thedye composition 358. The dye transfer sheet can then be heated to causeat least a portion of the dye composition to diffuse into theanisotropic coating layer 359.

The optical element including an anisotropic coating layer having atleast one alignment zone can be provided by purchasing the opticalelement from a third party manufacturer of optical elements or any othermanufacturer. The optical element can be provided to the producer by athird party manufacturer in prefabricated form. Prefabricated form meansthe optical element is already prepared with the anisotropic coatinglayer having at least one alignment zone already formed. For instance, athird party manufacturer can provide the producer with a prefabricatedlens blank comprising a anisotropic coating layer having at least onealignment zone. However, in other processes, the producer does notobtain the optical element comprising an anisotropic coating layerhaving at least one alignment zone from a third party manufacturer, andthe optical element comprising an anisotropic coating layer having atleast one alignment zone can instead be made by the producer. In thesescenarios, the producer can form an anisotropic coating layer with atleast one alignment zone on the optical element.

The optical element comprising an anisotropic coating layer having atleast one alignment zone can be made, either by the producer or a thirdparty manufacturer, using any suitable process, such as theabove-described processes.

After the producer obtains or makes the optical element comprising ananisotropic coating layer having at least one alignment zone, theanisotropic coating layer of the optical element is contacted with a dyecomposition. The producer can obtain at least one dye composition from athird party manufacturer of dye compositions or any other manufacturer.The dye composition can be a commercially pre-packaged composition. Thedye composition can comprise a dichroic dye and/or aphotochromic-dichroic dye and can optionally comprise a photochromic dyeand/or a conventional dye. Additional dye composition(s) can beobtained. Each additional dye composition can comprise a dichroic dyeand/or a photochromic-dichroic dye and/or a photochromic dye and/or aconventional dye. The dye composition and/or the additional dyecompositions can be obtained from the same third party manufacturer asthe third party manufacturer of the optical element comprising theanisotropic coating layer having at least one alignment zone (i.e. froma single commercial source). In another exemplary process, the dyecomposition and/or the additional dye compositions can be obtained froma different third party manufacturer as the third party manufacturer ofthe optical element comprising the anisotropic coating layer having atleast one alignment zone. In another exemplary process, the dyecomposition and/or the additional dye compositions can be made by theproducer.

The producer can contact the dye composition with the anisotropiccoating layer of the optical element to produce an optical article withgradient tint and gradient polarization by any appropriate method,including, but not limited to, spin coating, flow coating, spraycoating, dip dye method, use of a dye transfer substrate, curtaincoating, and any combination thereof.

Referring to FIGS. 10A-12, a dye solution can contact the anisotropiccoating layer of the optical element by a dip dye method. According tothe dip dye method of the present invention, an optical element 400comprising an anisotropic coating layer 402 having at least onealignment zone, is dipped into a bath 254 and contacted with a dyesolution 406. The bath 404 can be any container that can hold a dyesolution 406 and has sufficient size to allow the optical element 400comprising the anisotropic coating layer 402 to be dipped therein. Thedye solution can be held at any temperature, such as between 0° C. up toabout 200° C. The dye solution 406 can comprise dye composition(s) 432(shown in FIG. 14) including a dichroic dye and/or aphotochromic-dichroic dye (and optionally a photochromic dye or aconventional dye). There may be multiple baths 404 holding the dyesolution 406 and any additional dye solution. An additional dye solutioncan comprise dye composition(s) 432 including a dichroic dye and/or aphotochromic-dichroic dye and/or a photochromic dye and/or aconventional dye. In scenarios where there are multiple baths 404comprising dye solutions 406, the optical element 400 comprising theanisotropic coating layer 402 having at least one alignment zone can besequentially dipped into each of the prepared baths 404 to obtain thedesired effects.

According to the dip dye method, at least a portion of the opticalelement 400 comprising the anisotropic coating layer 402 is submerged(dipped) into the dye solution 406 of the dye composition(s) 432 of thebath 404. The optical element 400 can be of any type, as previouslymentioned, such as an optical lens, an ophthalmic lens, an opticalfilter, a window, a visor, a mirror, a display, and the like. FIGS. 10Aand 10C show several different types of optical elements 400 (i.e. acurved optical element 400 and a non-curved optical element 400). Theoptical element 400 can be dipped into the bath 404 in any orientation(as shown in FIGS. 10A-10D). For instance, the optical element 400 canbe dipped into the bath 404 while at an angle (see FIGS. 10A and 10D).In other examples, the optical element 400 can be dipped substantiallyhorizontally (see FIGS. 10B and 10C) or substantially vertically (notshown) or any orientation between substantially horizontally andsubstantially vertically. The orientation at which the optical element400 is dipped into the bath 404 can affect the tint gradient and thepolarization gradient on the resulting optical article.

Referring specifically to FIGS. 11A and 11B, the optical element 400having an anisotropic coating layer 402 can be dipped into the bath 404comprising a dye solution 406 by any means of submerging at least aportion of the optical element 400 in the dye solution 406. Forinstance, as shown in FIG. 11A, the optical element 400 can be manuallydipped (e.g., hand dipped) into the dye solution 406 by a user 408. Incontrast, as shown in FIG. 11B, the optical element 400 can beautomatically dipped into the dye solution 406 by, for instance, amechanical member 410 controlled by a controller 412.

Referring to FIG. 12, according to the dip dye method, at least aportion of the optical element 400 having the anisotropic coating layer402 is submerged in the dye solution 406. The portion of the opticalelement 400 submerged in the dye solution 406 depends on the desiredgradient tint and gradient polarization the producer wishes to impart onthe anisotropic coating layer 402 of the optical element 400. Forinstance, the optical element 400 may be either fully submerged in thedye solution 406, or only partially submerged in the dye solution 406(see FIG. 12).

According to the dip dye method, at least a portion of optical element400 having the anisotropic coating layer 402 is first submerged in thedye composition contained in the bath 404. The submerged optical element400 is then removed from the dye solution 406. The submerged opticalelement 400 can be removed from the dye solution 406 at a ratesufficient to provide a predetermined concentration gradient. Theprocess of submerging in and removing from the dye solution 406 may berepeated multiple times to achieve the desired tint and polarizationOptionally, the optical element 400 can be dipped into additional baths404 and withdrawn from additional dye solutions at a rate sufficient toprovide the predetermined concentration gradient. When the opticalelement 400 is dipped into the dye solution(s) 406, the dye solution 406diffuses into a three-dimensional polymeric matrix of the anisotropiccoating layer 402. The longer, or the more times, the optical element400 comprising the anisotropic coating layer 402 is submerged in the dyesolution 406, the more the dyes will diffuse into the polymeric matrix(i.e., the greater the tint and polarization). Because thethree-dimensional polymeric matrix of the first alignment zone of theanisotropic coating layer 402 is aligned in the first direction, thedyes also align in the first direction when they diffuse into thepolymeric matrix of the first alignment zone, providing polarization inthe first direction.

According to the dip dye method, the optical element 400 comprising theanisotropic coating layer 402 can be extracted from the dye solution 406at a predetermined rate to provide a predetermined concentrationgradient of the dyes diffused into the polymeric matrix of theanisotropic coating layer 402 along a length of the optical element.This can result in a predetermined tint gradient and polarizationgradient along the length of the optical element. In another example,the optical element 400 comprising the anisotropic coating layer 402 canbe extracted at different rates as it is being removed from the dyesolution 406. For instance, the optical element 400 comprising theanisotropic coating layer 402 can be fully submerged in the dye solution406. A first portion of the optical element 400 can be removed from thedye solution 406 at one rate, and then a second portion of the opticalelement 400 can be removed at another rate (i.e. the speed at which theoptical element 400 is removed changes before the entire optical element400 is removed). There may also be pauses during the removal of theoptical element 400 from the dye solution 406 so as to allow theremaining submerged portion to absorb more dyes before the remainingportion of the optical element 400 is removed from the dye solution 406.An optical element 400 removed at a constant rate can have a continuoustint gradient and polarization gradient, while varying the rate at whichthe optical element 400 is removed from the dye composition can create anon-continuous a tint gradient and polarization gradient (i.e. a stepgradient).

Referring to FIG. 13, a dye composition can contact the anisotropiccoating layer 402 of the optical element 400 by contacting theanisotropic coating layer 402 with a dye transfer substrate 414comprising a gradient layer of dye composition 416. The dye transfersubstrate can be a sheet, such as a flexible sheet configured to holdthe gradient layer of dye composition 416, yet allow the gradient layerof dye composition 416 to transfer to an adhered surface upon heating ofthe dye transfer substrate 416. A gradient layer of dye composition 416can contact the anisotropic coating layer 402 of the optical element 400by applying a side of the dye transfer substrate 414 comprising thegradient layer of dye composition 416 against the anisotropic coatinglayer 402. Optionally, a securing means 418 can be secured to a side ofthe dye transfer substrate 414 opposite the side of the dye transfersubstrate having a gradient layer of dye composition 416 so that thegradient layer of dye composition 416 cannot slide while in contact withthe anisotropic coating layer 402. The securing means 418 can be anymaterial sufficient to secure the gradient layer of dye composition 416to the anisotropic coating layer 402 so that neither can slide. Forinstance, the securing means 418 can be a heavy material such as a metalplate. When the dye transfer substrate 414 comprising the gradient layerof dye composition 416 is applied against the coating, the dye transfersubstrate 414 is heated by a heater 420. The heater 420 can be any meansto heat the dye transfer substrate 414 to a sufficient temperature thatallows the dyes to diffuse into the anisotropic coating layer 402 inaccordance with the gradient layer of dye composition 416. In anotherexample, the gradient layer of dye composition 416 can be diffused intothe anisotropic coating layer 402 by applying pressure the contacted dyetransfer substrate 414 and anisotropic coating layer 402. Once a desiredamount of the dyes have transferred from the dye transfer substrate 414to the anisotropic coating layer 402, the dye transfer substrate 414 canbe removed.

A consumer can contact the producer to order an optical article havinggradient tint and gradient polarization. The consumer may be anindividual consumer or a commercial consumer. In one example, theconsumer desires an optical article, such as optical lenses, having agradient tint and a gradient polarization and contacts the producer tohave the optical lenses made. The optical lenses can be installed intoeyeglass frames to form eyeglasses. In some examples, the consumer canbe the wearer of the optical article, such as a wearer of eyeglasses.

The producer can obtain from the consumer desired product propertyinformation. The desired product property information can includedesired fixed tint gradient, desired activated tint gradient, desiredfixed polarization gradient, and desired activated polarizationgradient. Fixed tint gradient and fixed polarization gradient refer tothe tint and polarization of the optical article that is not exposed toactinic radiation, such as UV radiation. Activated tint gradient andactivated polarization gradient refer to the tint and polarization ofthe optical article upon exposure to actinic radiation. Certain desiredproduct property information can depend on the type of optical articledesired by the consumer. For instance, a consumer desiring opticallenses having a gradient tint and gradient polarization may providefurther desired product property information, such as prescriptionstrength, choice of eyeglass frames, tint color, additional colorant,amount of optical lens to be covered by the gradient tint, and amount ofthe optical lens covered by the gradient polarization.

The above-described process can be carried out in light of the desiredproperty information collected from the consumer. The producer canprovide the optical element comprising an anisotropic coating layerhaving at least one alignment zone and contact the coating with a dyecomposition, in order to make an optical article that matches thecustomer's specifications. To meet the customer's desired product needs,additional steps may be taken by the producer, or its third partymanufacturers. For instance, for a customer ordering lenses foreyeglasses, the lens may need to be cut and ground to the correct sizeand specifications. In another example, this may require furtherpreparation of the optical article before it is provided to theconsumer. For instance, a hard coating may be applied over the opticalarticle to protect the optical article, such as from scratches. Inanother example, the consumer may desire two optical articles, such asoptical lenses, which may be installed into the consumer's choseneyeglass frames before the optical articles are provided to theconsumer.

Referring to FIG. 14, the producer may obtain a kit 430 for making anoptical article having a gradient tint and gradient polarization. Thekit 430 may include an optical element 400 comprising an anisotropiccoating layer 402 having at least one alignment zone. This opticalelement 400 comprising the anisotropic coating layer 402 may be thepreviously described prefabricated optical element 400 comprising theanisotropic coating layer 402 (i.e. the kit 430 comprises the opticalelement 400 with the anisotropic coating layer 402 already applied tothe optical element 400 before the kit 430 is obtained by the producer).The kit 430 may further comprise dye composition(s) 432. At least one ofthe dye compositions 432 comprises a dichroic dye and/or aphotochromic-dichroic dye (and optionally a photochromic dye or aconventional dye). The kit 430 may comprise additional dye compositions,which may include a dichroic dye and/or a photochromic-dichroic dyeand/or a photochromic dye and/or a conventional dye. The kit 430 maycomprise a pre-mixed solution comprising a dye composition(s). The kit430 may also comprise a dye transfer substrate 414 comprising a gradientlayer of dye composition 416. The kit 430 may comprise a plurality ofdye transfer substrates 414 having a gradient layer of dye composition416, allowing the dye composition 432 contacted with the coating 402 ofthe optical element 400 to include different gradients of tint andpolarization. The kit 430 may further comprise instructions 434 forcontacting the dye composition 432 with the anisotropic coating layer402 of the optical element 400, in order to form a predeterminedconcentration gradient. The kit 430 may be used by the producer to makean optical article 200 having a gradient tint and a gradientpolarization by any of the above-described methods.

The instructions 434 for contacting the dye composition with theanisotropic coating layer to form a predetermined concentration gradientcan be obtained by the consumer. The instructions 434 can includeinformation such as, but not limited to, type(s) of optical elementcomprising the anisotropic coating layer having at least one alignmentzone to use, type(s) of dye compositions to use, how to prepare a dyesolution from the dye composition(s), method of contacting the dyesolution with the anisotropic coating layer of the optical element,duration of contact required between the dye solution and theanisotropic coating layer of the optical element, additional processsteps to produce the optical article once the dye solution has contactedthe anisotropic coating layer of the optical element, etc. Theinstructions 434 can be obtained from the same third party manufactureras the third party manufacturer of the optical element comprising theanisotropic coating layer having at least one alignment zone and the dyecomposition(s) (i.e. from a single commercial source). In anotherexemplary process, the instructions 434 can be obtained from a differentthird party producer or manufacturer as the third party manufacturer ofthe optical element comprising the anisotropic coating compositionhaving at least one alignment zone and the dye compositions. In anotherexemplary process, the instructions 434 can be developed by theproducer.

An optical article having a gradient tint and gradient polarization canbe prepared from by any of the methods previously described.

The following examples are presented to demonstrate the generalprinciples of the invention. The invention should not be considered aslimited to the specific examples presented. All parts and percentages inthe examples are by weight unless otherwise indicated.

Example 1 Part 1—Preparation of the Primer Layer Formulation (PLF)

Into a suitable container equipped with a magnetic stir-bar thefollowing materials were added in the amounts indicated in the followingTable 1.

TABLE 1 Primer Layer Formulation Component Amount Polyacrylate polyol¹6.687 g POLYMEG ® 1000² 16.65 g DESMODUR ® PL 340³ 21.90 g TRIXENE ® BI7960⁴ 15.62 g BYKO-333⁵ 0.034 g K-KAT ® 348⁶ 0.454 gGamma-Glycidoxypropyltrimethoxysilane  1.79 g TINUVIN ® 144⁷ 0.757 gIRGANOX ® 245⁸ 0.757 g Dipropylene Glycol Methyl Ether Acetate 32.77 g¹According to composition D of Example 1 in U.S. Pat. 6,187,444replacing styrene with methyl methacrylate and 0.5% by weight oftriphenyl phosphite was added. ²A polyalkylenecarbonate diol availablefrom Great Lakes Chemical Corp. ³A blocked aliphatic polyisocyanateavailable from Covestro AG. ⁴A blocked trifunctional urethanecrosslinker available from Baxenden Chemicals, Ltd ⁵A polyether modifiedpolydimethylsiloxane available from BYK Chemie, USA ⁶A bismuthcarboxylate catalyst available from King Industries. ⁷A hindered aminelight stabilizer available from BASF Corporation. ⁸An antioxidantavailable from BASF Corporation.

The mixture was stirred at room temperature for 2 hours to yield asolution having 51.47 weight % final solids based on the total weight ofthe solution.

Part 2—Preparation of Liquid Crystal Alignment Formulation (LCAF)

A photoalignment material described in US Patent Application PublicationNo. US 2011/0135850 A1 as a Comparative Example was prepared by adding 6weight percent of the photoalignment material to cyclopentanone, basedon the total weight of the solution. This mixture was allowed to stiruntil the photoalignment material was completely dissolved.

Part 3—Preparation of the Anisotropic Layer Formulation (CLF)

An anisotropic layer formulation was prepared by combining the materialsindicated in the following Table 2 and stirring for two hours at 80° C.to yield a homogeneous solution, then cooled to room temperature. Allquantities are reported as parts by weight.

TABLE 2 Anisotropic Layer Formulation CLF-1 Component CLF-1 Anisole19.50 BYK ®-322¹ 0.020 4-Methoxyphenol 0.030 RM257² 12.60 LCM-2³ 6.60LCM-3⁴ 5.40 LCM-4⁵ 5.40 IRGACURE ® 819⁶ 0.45 PCDD 1⁷ 1.26 PCDD 2⁸ 2.34¹An aralkyl modified poly-methyl-alkyl-siloxane available from BYKChemie, USA. ²A liquid crystal monomer4-(3-acryloyloxypropyloxy)-benzoic acid 2-methyl-1,4-phenylene ester,available commercially from EMD Chemicals, Inc.³1-(6-(6-(6-(6-(6-(6-(6-(6-(8-(4-(4-((1r,1′s,4R,4′R)-4′-pentyl-[1,1′-bi(cyclohexane)]-4-carbonyloxy)2-or3-methylphenyloxycarbonyl)phenoxy)octyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-2-methylprop-2-en-1-oneprepared according to procedures described in U.S. Pat. No. 7,910,019B2.⁴1-(6-(6-(6-(6-(6-(6-(6-(6-(8-(4-(4-(4-(6-acryloyloxyhexyloxy)benzoyloxy)phenoxycarbonyl)phenoxy)octyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexanol,prepared in accordance with Example 17 in U.S. Pat. No. 7,910,019B2.⁵4-(((1s,40-r-pentylcyclohexane-1-carbonyl)oxy)phenyl4-((6-(acryloyloxy)hexyl)oxy)benzoate. ⁶A photoinitiator available fromBASF Corporation. ⁷A photochromic dichroic dye of structure3,3-bis(4-methoxyphenyl)-6-methoxy-7-(4-(4-(trans,trans-4′-pentyl-[1,1′-bi(cyclohexane)1-4-carbonyloxy)phenyl)piperazin-1-yl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyranprepared according to the procedure of example 44 in U.S. Pat. No.8,518,546B2. ⁸A photochromic dichroic dye of structure3-phenyl-3-(4-morpholinophenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-6-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyranprepared in accordance with Example 33 in U.S. Pat. No. 8,545,984B2.

Part 4—Procedures Used for Preparing the Substrate with AlignedAnistropic Layer

Corona Treatment:

Where indicated below, prior to the application of any of the reportedcoating layers, the substrate or coated substrate was subject to coronatreatment by passing on a conveyor belt in a Tantec EST Systems PowerGenerator HV 2000 series corona treatment apparatus having a highvoltage transformer. The substrates were exposed to corona generated at1288 Watts, while traveling on a conveyor at a belt speed 3.8 ft/minute.

Substrate Preparation:

Lens substrates of CR-39® SFSV Base 4.25 with a diameter of 75 mm wereobtained from Essilor. Each substrate was cleaned by wiping with atissue soaked with acetone, dried with a stream of air and coronatreated as described above.

Coating Procedure for the Primer Layer:

The PLF was applied to the prepared lens by dispensing approximately 1.5mL of the solution and spinning the substrates at 500 revolutions perminute (rpm) for 2 seconds, followed by 2500 rpm for 2.2 secondsyielding a target film thickness of 4.5 microns. Afterwards, the coatedsubstrates were placed in an oven maintained at 125° C. for 60 minutes,then cooled to room temperature. The coated substrates were then coronatreated as described above.

Coating Procedure for the Liquid Crystal Alignment Layer:

The LCAF was applied to the test substrates by spin-coating on a portionof the surface of the test substrate by dispensing approximately 1.0 mLof the solution and spinning the substrates at 600 revolutions perminute (rpm) for 2 seconds, followed by 2,400 rpm for 2 seconds yieldinga target film thickness of less than one micron. Afterwards, the coatedsubstrates were placed in an oven maintained at 120° C. for 15 minutes,then cooled to room temperature.

The dried photoalignment layer on each of the substrates was at leastpartially ordered by exposure to linearly polarized ultravioletradiation. The light source was oriented such that the radiation waslinearly polarized in a plane perpendicular to the surface of thesubstrate. The amount of ultraviolet radiation that each photoalignmentlayer was exposed to was measured using a UV POWER PUCK™ High energyradiometer from EIT Inc., and was as follows: UVA 0.020 W/cm² and 0.298J/cm²; UVB 0.010 W/cm² and 0.132 J/cm²; UVC 0.002 W/cm² and 0.025 J/cm²;and UVV 0.025 W/cm² and 0.355 J/cm². After ordering at least a portionof the photo-orientable polymer network, the substrates were cooled toroom temperature and kept covered, and were not subject to coronatreatment.

Coating Procedure for the Anisotropic Layer:

The Anisotropic Layer Formulations CLF-1 was applied by spin coating ata rate of 500 revolutions per minute (rpm) for 2 seconds, followed by1500 rpm for 1.3 seconds onto the at least partially orderedphotoalignment materials on the lens substrates, yielding a target filmthickness of approximately 20 microns. Each coated substrate was placedin an oven at 60° C. for 30 minutes. Afterwards they were cured undertwo ultraviolet lamps in a UV Curing Oven Machine designed and built byBelcan Engineering under a nitrogen atmosphere while moving continuouslyon a conveyor belt operating at a linear rate of 61 cm/minute (2ft/minute). The oven operated at peak intensity of 0.388 Watts/cm² ofUVA and 0.165 Watts/cm² of UVV and UV dosage of 7.386 Joules/cm² of UVAand 3.337 Joules/cm² of UVV.

Part 5—Preparation of Gradient Tint/Gradient Polarization OpticalArticle

A solution of dichroic dye was prepared using the ingredients in Table 3

TABLE 3 Dichroic Dye Formulation Amount Component (Parts by weight)Hydroxypropyl cellulose 57.6 HI-SIL ® T-700¹ 19.2 Diglyme 168Tetrahydrofurfuryl alcohol 144 Propylene glycol n-butyl ether 96Aromatic 100 480 Dichroic Dye² 40 ¹A thickener available from PPGIndustries, Inc. ²A magenta fixed tint, polyazo dichroic dyecorresponding to compound 1c in the following reference: Shigeo YASUI,Masaru MATSUOKA, Teijiro KITAO; Journal of the Japan Society of ColourMaterial, Vol. 61, (1988) No. 12, pp. 678-684.

The resulting tinted suspension was loaded in an airbrush with airpressure set to 20 psi. A lens, prepared in parts 1-4 above, wassupported at an angle of 45° from vertical, and oriented such that theanisotropic layer alignment was oriented horizontally. The dichroic dyesolution was sprayed onto the lens, using a horizontal back and forthmotion, starting at the top and moving toward the bottom, such that thedichroic dye solution was applied thickest at the top and thinnest atthe bottom. The coated lens was then placed in a thermal oven at 100° C.for 900 seconds. After cooling, the lens was rinsed with methanol toremove resin and residual dye. The lens produced demonstrated a gradienttint as well as a gradient polarization property. This is furtherdemonstrated in the following figures. FIG. 15 shows the lensilluminated from behind with unpolarized light, exhibiting a visibletint gradient. FIG. 16 shows the passage of light through the lens whena polarizer which is oriented parallel (0°) to the alignment of theanisotropic layer. FIG. 17 shows the passage of light through the samelens when the polarizer is oriented perpendicular (90°) to the directionof alignment of the anisotropic coating layer.

Part 6—Preparation of Uniform Tint, Gradient Polarization Article

A solution of conventional dye was prepared using the ingredients inTable 4

TABLE 4 Conventional Dye Formulation Amount Component (Parts by weight)Hydroxypropyl cellulose 57.6 HI-SIL ® T-700 19.2 Diglyme 168Tetrahydrofurfuryl alcohol 144 Propylene glycol n-butyl ether 96Aromatic 100 480 Conventional Magenta dye 40

To this was added the Aromatic 100 and conventional dye. The suspensionwas mixed until the dye dissolved.

The suspension of dichroic dye prepared in Part 5 was loaded in anairbrush with air pressure set to 20 psi. A lens, prepared in parts 1-4above, was supported at an angle of 45° from vertical, and oriented suchthat the anisotropic layer alignment was oriented horizontally. Thedichroic dye formulation was sprayed onto the lens, using a horizontalback and forth motion, starting at the top and moving toward the center,such that the dichroic dye suspension was applied thickest at the top,thinnest at the center and the bottom remained uncoated.

The suspension of conventional dye prepared in Table 4 above was loadedin a second airbrush with air pressure set to 20 psi. The conventionaldye formulation was sprayed onto the lens, using a horizontal back andforth motion, starting at the bottom and moving upward toward thecenter, such that the conventional dye formulation was applied thickestat the bottom, thinnest at the center, and was absent at the top, withoverlap of the dichroic and conventional dye formulations in the centerof the lens.

The coated lens was then placed in a thermal oven at 100° C. for 900seconds. After cooling, the lens was rinsed with methanol to removeresin and residual dye. The lens produced demonstrated a uniform tintacross the surface of the lens, as well as a gradient polarizationproperty. This is further demonstrated in the following figures. FIG. 18shows the lens illuminated from behind with unpolarized light,exhibiting a uniform tint. FIG. 19 shows the passage of light throughthe lens when a polarizer which is oriented parallel (0°) to thealignment of the anisotropic layer. FIG. 20 shows the passage of lightthrough the same lens when the polarizer is oriented perpendicular (90°)to the direction of alignment of the anisotropic coating layer.

Example 2 Part 1—Preparation of the Primer Layer Formulation (PLF)

Into a suitable container equipped with a magnetic stir-bar thefollowing materials were added in the amounts indicated in the followingTable 5.

TABLE 5 Primer Layer Formulation Component Amount Polyacrylate polyol¹6.687 g POLYMEG ® 1000² 16.65 g DESMODUR ® PL 340³ 21.90 g TRIXENE ® BI7960⁴ 15.62 g BYKO-333⁵ 0.034 g K-KAT ® 348⁶ 0.454 gGamma-Glycidoxypropyltrimethoxysilane  1.79 g TINUVIN ® 144⁷ 0.757 gIRGANOX ® 245⁸ 0.757 g Dipropylene Glycol Methyl Ether Acetate 32.77 g¹According to composition D of Example 1 in U.S. Pat. 6,187,444replacing styrene with methyl methacrylate and 0.5% by weight oftriphenyl phosphite was added. ²A polyalkylenecarbonate diol availablefrom Great Lakes Chemical Corp. ³A blocked aliphatic polyisocyanateavailable from Covestro AG. ⁴A blocked trifunctional urethanecrosslinker available from Baxenden Chemicals, Ltd ⁵A polyether modifiedpolydimethylsiloxane available from BYK Chemie, USA ⁶A bismuthcarboxylate catalyst available from King Industries. ⁷A hindered aminelight stabilizer available from BASF Corporation. ⁸An antioxidantavailable from BASF Corporation.

The mixture was stirred at room temperature for 2 hours to yield asolution having 51.47 weight % final solids based on the total weight ofthe solution.

Part 2—Preparation of Liquid Crystal Alignment Formulation (LCAF)

A photoalignment material described in US Patent Application PublicationNo. US 2011/0135850 A1 as a Comparative Example was prepared by adding 6weight percent of the photoalignment material to cyclopentanone, basedon the total weight of the solution. This mixture was allowed to stiruntil the photoalignment material was completely dissolved.

Part 3—Preparation of the Anisotropic Layer Formulation (CLF)

An anisotropic layer formulation was prepared by combining the materialsindicated in the following Table 6 and stirring for two hours at 80° C.to yield a homogeneous solution, then cooled to room temperature. Allquantities are reported as parts by weight.

TABLE 6 Anisotropic Layer Formulation CLF-1 Component CLF-1 Anisole19.50 BYK ®-322¹ 0.020 4-Methoxyphenol 0.030 RM257² 12.60 LCM-2³ 6.60LCM-3⁴ 5.40 LCM-4⁵ 5.40 IRGACURE ® 819⁶ 0.45 PCDD 1⁷ 1.26 PCDD 2⁸ 2.34¹An aralkyl modified poly-methyl-alkyl-siloxane available from BYKChemie, USA. ²A liquid crystal monomer4-(3-acryloyloxypropyloxy)-benzoic acid 2-methyl-1,4-phenylene ester,available commercially from EMD Chemicals, Inc.³1-(6-(6-(6-(6-(6-(6-(6-(6-(8-(4-(4-((1r,1′s,4R,4′R)-4′-pentyl-[1,1′-bi(cyclohexane)]-4-carbonyloxy)2-or3-methylphenyloxycarbonyl)phenoxy)octyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-2-methylprop-2-en-1-oneprepared according to procedures described in U.S. Pat. No. 7,910,019B2.⁴1-(6-(6-(6-(6-(6-(6-(6-(6-(8-(4-(4-(4-(6-acryloyloxyhexyloxy)benzoyloxy)phenoxycarbonyl)phenoxy)octyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexanol,prepared in accordance with Example 17 in U.S. Pat. No. 7,910,019B2.⁵4-(((1s,4r)-r-pentylcyclohexane-1-carbonyl)oxy)phenyl4-((6-(acryloyloxy)hexyl)oxy)benzoate. ⁶A photoinitiator available fromBASF Corporation. ⁷A photochromic dichroic dye of structure3,3-bis(4-methoxyphenyl)-6-methoxy-7-(4-(4-(trans,trans-4′-pentyl-[1,1′-bi(cyclohexane)]-4-carbonyloxy)phenyl)piperazin-1-yl)-10,12-di(trifluoromethyl)-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyranprepared according to the procedure of example 44 in U.S. Pat. No.8,518,546B2. ⁸A photochromic dichroic dye of structure3-phenyl-3-(4-morpholinophenyl)-10-[4-(4-(4-(trans-4-pentylcyclohexyl)phenyl)benzamido)phenyl]-6-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyranprepared in accordance with Example 33 in U.S. Pat. No. 8,545,984B2.

Part 4—Procedures Used for Preparing the Substrate with AlignedAnistropic Layer

Corona Treatment:

Where indicated below, prior to the application of any of the reportedcoating layers, the substrate or coated substrate was subject to coronatreatment by passing on a conveyor belt in a Tantec EST Systems PowerGenerator HV 2000 series corona treatment apparatus having a highvoltage transformer. The substrates were exposed to corona generated at1288 Watts, while traveling on a conveyor at a belt speed 3.8 ft/minute.

Substrate Preparation:

Lens substrates of CR-39® SFSV Base 4.25 with a diameter of 75 mm wereobtained from Essilor. Each substrate was cleaned by wiping with atissue soaked with acetone, dried with a stream of air and coronatreated as described above.

Coating Procedure for the Primer Layer:

The PLF was applied to the prepared lens by dispensing approximately 1.5mL of the solution and spinning the substrates at 500 revolutions perminute (rpm) for 2 seconds, followed by 2500 rpm for 2.2 secondsyielding a target film thickness of 4.5 microns. Afterwards, the coatedsubstrates were placed in an oven maintained at 125° C. for 60 minutes,then cooled to room temperature. The coated substrates were then coronatreated as described above.

Coating Procedure for the Liquid Crystal Alignment Layer:

The LCAF was applied to the test substrates by spin-coating on a portionof the surface of the test substrate by dispensing approximately 1.0 mLof the solution and spinning the substrates at 600 revolutions perminute (rpm) for 2 seconds, followed by 2,400 rpm for 2 seconds yieldinga target film thickness of less than one micron. Afterwards, the coatedsubstrates were placed in an oven maintained at 120° C. for 15 minutes,then cooled to room temperature.

The dried photoalignment layer on each of the substrates was at leastpartially ordered by exposure to linearly polarized ultravioletradiation. The light source was oriented such that the radiation waslinearly polarized in a plane perpendicular to the surface of thesubstrate. The amount of ultraviolet radiation that each photoalignmentlayer was exposed to was measured using a UV POWER PUCK™ High energyradiometer from EIT Inc., and was as follows: UVA 0.020 W/cm² and 0.298J/cm²; UVB 0.010 W/cm² and 0.132 J/cm²; UVC 0.002 W/cm² and 0.025 J/cm²;and UVV 0.025 W/cm² and 0.355 J/cm². After ordering at least a portionof the photo-orientable polymer network, the substrates were cooled toroom temperature and kept covered, and were not subject to coronatreatment.

Coating Procedure for the Anisotropic Layer:

The Anisotropic Layer Formulations CLF-1 was applied by spin coating ata rate of 500 revolutions per minute (rpm) for 2 seconds, followed by1500 rpm for 1.3 seconds onto the at least partially orderedphotoalignment materials on the lens substrates, yielding a target filmthickness of approximately 20 microns. Each coated substrate was placedin an oven at 60° C. for 30 minutes. Afterwards they were cured undertwo ultraviolet lamps in a UV Curing Oven Machine designed and built byBelcan Engineering under a nitrogen atmosphere while moving continuouslyon a conveyor belt operating at a linear rate of 61 cm/minute (2ft/minute). The oven operated at peak intensity of 0.388 Watts/cm² ofUVA and 0.165 Watts/cm² of UVV and UV dosage of 7.386 Joules/cm² of UVAand 3.337 Joules/cm² of UVV.

Part 5—Dip Coating Procedure

A solution of dichroic dyes was prepared by using the ingredients inTable 7.

TABLE 7 Dichroic Dye Formulation Component Amount Aromatic 100  800 gDichroic Dye¹  2.0 g ¹A fixed tint, polyazo dichroic dye correspondingto compound 1c in the following reference: Shigeo YASUI, MasaruMATSUOKA, Teijiro KITAO; Journal of the Japan Society of ColourMaterial, Vol. 61, (1988) No. 12, pp. 678-684.

The solution was placed in a beaker and heated to 65° C. The lensprepared above was placed a clamp attached to the edges of the lens,which was held perpendicular to the solution, and the anisotropic layeralignment was oriented parallel to the surface of the solution. The lenswas submerged fully into the solution for 3 seconds, then raised suchthat 30 mm of the lens was held above the solution. The lens was thendipped +/−10 mm from this position for three minutes at a rate of 125cycles per minute. The lens was then fully submerged for 3 seconds, theremoved from the solution. After release from the clamp, whilemaintaining the horizontal orientation of the anisotropic layeralignment, the lens was secured at an angle of 10° from vertical andplaced in an oven at 100° C. for 120 seconds. After cooling, the lenswas rinsed with methanol to remove residual dye. The lens produceddemonstrated a gradient tint as well as a gradient polarizationproperty. This is further demonstrated in the following figures. Bothfigures show the lens which is backlit through a polarizing filter. FIG.21 shows the passage of light through the lens when a polarizer which isoriented parallel (0°) to the alignment of the anisotropic layer. FIG.22 shows the passage of light through the same lens when the polarizeris oriented perpendicular (90°) to the direction of alignment of theanisotropic coating layer.

It will be readily appreciated by those skilled in the art thatmodifications as indicated above may be made to the invention withoutdeparting from the concepts disclosed in the foregoing description.Accordingly, the particular embodiments described in detail herein areillustrative only and are not limiting to the scope of the invention,which is to be give the full breadth of the appended claims and any andall equivalents thereof.

The invention claimed is:
 1. A method of making an optical articlehaving multiple light-influencing zones, comprising: forming analignment coating layer comprising a first alignment region and a secondalignment region over at least a portion of an optical element; whereinthe first alignment region and the second alignment region of thealignment coating layer are formed by: applying an alignment coatingcomposition over at least a portion of a first major surface of theoptical element; masking a second portion of the alignment coatingcomposition with a masking component that blocks a first polarizedradiation prior to exposing a first portion of the alignment coatingcomposition to the first polarized radiation; exposing the first portionof the alignment coating composition to the first polarized radiationhaving a first polarizing direction to form the first alignment regionof the alignment coating layer; exposing the second portion of thealignment coating composition to the second polarized radiation having asecond polarizing direction that is different from the first polarizingdirection to form the second alignment region of the alignment coatinglayer; applying at least one anisotropic material over the firstalignment region and the second alignment region by an inkjet printingdevice; and applying at least one dichroic material and/or at least onephotochromic-dichroic material over at least one of the first alignmentregion and the second alignment region to form a first light-influencingzone over the first alignment region and a second light-influencing zoneover the second alignment region.
 2. The method of claim 1, furthercomprising applying at least one photochromic material over at least oneof the first alignment region and the second alignment region.
 3. Themethod of claim 1, wherein the optical element comprises a first majorsurface and the first alignment region and the second alignment regionare formed on the first major surface of the optical element.
 4. Themethod of claim 3, wherein the first major surface is a curved surface.5. The method of claim 1, wherein the optical element is an opticallens.
 6. The method of claim 1, wherein the alignment coatingcomposition is applied by a method selected from the group consisting ofspin coating, spray coating, dip coating, and curtain coating.
 7. Themethod of claim 1, wherein the alignment coating composition comprisesat least one photo-alignment material.
 8. The method of claim 1, furthercomprising removing the masking component from the second portion of thealignment coating composition prior to exposing the second portion ofthe alignment coating composition to the second polarized radiation. 9.The method of claim 1, further comprising masking the first portion ofthe alignment coating composition with a masking component that blocksthe second polarized radiation after exposing the first portion of thealignment coating composition to the first polarized radiation.
 10. Themethod of claim 1, wherein the anisotropic material comprises at leastone polymerizable liquid crystal material.
 11. The method of claim 1,wherein the at least one dichroic material and/or the at least onephotochromic-dichroic material, and optionally at least one photochromicmaterial, are applied by the inkjet printing device.
 12. The method ofclaim 11, wherein the inkjet printing device comprises a printing headconnected to a source of anisotropic material and connected to at leastone additional source selected from the group consisting of a source ofdichroic material, a source of photochromic-dichroic material, and,optionally, a source of photochromic material.
 13. The method of claim12, wherein the anisotropic material, the at least one dichroic materialand/or at least one photochromic-dichroic material, and, optionally, thephotochromic material are applied by: scanning the printing head overthe optical element; and dispensing a controlled amount of theanisotropic material, the at least one dichroic material and/or the atleast one photochromic-dichroic material, and, optionally, thephotochromic material onto the optical element to form a coatingcomposition over a selected area of the optical element.
 14. The methodof claim 13, wherein the amount of at least one of the dichroicmaterial, the photochromic-dichroic material, and the optionalphotochromic material is uniformly distributed across at least one ofthe first light-influencing zone and the second light-influencing zone.15. The method of claim 13, wherein the amount of at least one of thedichroic material, the photochromic-dichroic material, and the optionalphotochromic material varies across at least one of the firstlight-influencing zone and the second light-influencing zone.
 16. Themethod of claim 1, further comprising curing the anisotropic material.17. The method of claim 1, further comprising forming at least oneadditional alignment region on the optical element.
 18. The method ofclaim 17, wherein the first alignment region, the second alignmentregion, and the at least one additional alignment region of thealignment coating layer are formed by: applying an alignment coatingcomposition over at least a portion of a first major surface of theoptical element; exposing a first portion of the alignment coatingcomposition to a first polarized radiation having a first polarizingdirection to form the first alignment region; exposing a second portionof the alignment coating composition to a second polarized radiationhaving a second polarizing direction that is different from the firstpolarizing direction to form the second alignment region; exposing atleast one additional portion of the alignment coating composition topolarized radiation having a polarizing direction that is the same ordifferent than the first polarizing direction and/or the secondpolarizing direction to form the at least one additional alignmentregion.
 19. A method of making an optical article having multiplelight-influencing zones, comprising: forming an alignment coating layercomprising a first alignment region and a second alignment region overat least a portion of an optical element; wherein the first alignmentregion and the second alignment region of the alignment coating layerare formed by: applying an alignment coating composition over at least aportion of a first major surface of the optical element; exposing afirst portion of the alignment coating composition to a first polarizedradiation having a first polarizing direction to form the firstalignment region of the alignment coating layer; exposing a secondportion of the alignment coating composition to a second polarizedradiation having a second polarizing direction that is different fromthe first polarizing direction to form the second alignment region ofthe alignment coating layer; applying an anisotropic material over thealignment coating layer by an inkjet printing device; and applying atleast one of a dichroic material and a photochromic-dichroic materialover the alignment coating layer in a predetermined pattern to form atleast two light-influencing zones in the predetermined pattern.
 20. Themethod of claim 19, wherein the anisotropic material comprises at leastone polymerizable liquid crystal material.
 21. The method of claim 19,further comprising applying at least one photochromic material over atleast one of the first alignment region and the second alignment region.22. The method of claim 19, wherein the at least one dichroic materialand/or the at least one photochromic-dichroic material, and optionallyat least one photochromic material, are applied by the inkjet printingdevice.
 23. The method of claim 22, wherein the inkjet printing devicecomprises a printing head connected to a source of anisotropic material,and connected to at least one additional source selected from the groupconsisting of a source of dichroic material, a source ofphotochromic-dichroic material, and, optionally, a source ofphotochromic material.
 24. The method of claim 23, wherein theanisotropic material, the at least one dichroic material and/or at leastone photochromic-dichroic material, and, optionally, the photochromicmaterial are applied by: scanning the printing head over the opticalelement; and dispensing a controlled amount of the anisotropic material,the at least one dichroic material and/or the at least onephotochromic-dichroic material, and, optionally, the photochromicmaterial onto the optical element to form a coating composition over aselected area of the optical element.